THE  HYDROGENATION 
OF  OILS 

CATALYZERS  AND  CATALYSIS 

AND 

THE  GENERATION  OF  HYDROGEN  AND  OXYGEN 


BY 

CARLETON    ELLIS,    S.  B. 

CO-AUTHC?R   OF 

"ULTRA-VIOLET  LIGHT:  ITS  APPLICATION  IN  CHEMICAL  ARTS" 

Member  of  American  Chemical  Society,  American  Institute  Chemical  Engineers, 

American  Electrochemical  Society,  Franklin  Institute,  New  Jersey  Chemical 

Society,  Inventors'  Guild,  Society  of  Chemical  Industry  (London) , 

Fellow  of  Chemical  Society  and  President  of 

New  Jersey  Chemical  Society 


SECOND    EDITION 
Thoroughly  Revised  and  Enlarged 


240  Illustrations 


NEW  YORK 
D.  VAN  NOSTRAND   COMPANY 

25  PARK  PLACE 
1919 


COPYRIGHT,  1914,  1919 

BY 

D.  VAN  NOSTRAND  COMPANY 


PREFACE   TO   THE   SECOND   EDITION 


SINCE  the  first  edition  of  this  volume  was  published  in  1914,  the 
strides  made  in  the  oil-hardening  industry  have  surpassed  all  expec- 
tations. The  advances  effected  by  inventors  in  simplifying  old  methods 
and  creating  new  ones  and  the  wider  adaptation  of  the  process  in  the 
hands  of  skillful  factory  operators  have  led  to  many  changes  and 
betterments.  The  present  edition  endeavors  to  bring  the  develop- 
ments in  this  field  down  to  date,  and  to  offer  suggestions  of  future 
possibilities.  Unexpected  uses  for  hydrogenated  oils  have  been  and 
continue  to  be  discovered,  hence  the  market  for  these  fats  is  constantly 
broadening.  After  finding  a  secure  place  for  the  production  of  edible  fats 
in  this  country,  the  hydrogenation  process  has  also  been  taken  up  more 
seriously  by  the  soap-maker,  and  with  the  scarcity  of  natural  tallow 
due  to  war  conditions,  has  enabled  the  soap  manufacturer  to  produce 
an  artificial  tallow  from  relatively  cheap  oils.  During  the  past  two 
years  this  has  been  accomplished  on  a  large  scale. 

Much  of  historical  and  general  interest  will  be  found  in  the  records 
of  patent  litigation  in  this  country,  appearing  in  the  appendix.  The 
details  of  the  beginning  of  oil  hardening  in  the  United  States,  which 
hitherto  seemingly  have  been  surrounded  by  a  veil  of  mystery,  are 
now  accessible  to  the  reader. 

Owing  to  certain  difficulties  of  classification,  an  unusually  com- 
plete index  is  appended. 

C.  E. 

92  GREENWOOD  AVENUE, 

MONTCLAIR,  N.  J. 

Dec.  1,  1918. 

in 


405706 


vi  PREFACE  TO  THE  FIRST  EDITION 

so  later,  Sabatier  and  Senderens  reversed  this  procedure  and  made 
such  nickel  carry  hydrogen  to  unsaturated  organic  compounds  of  a 
character  which  could  be  vaporized  readily.  Then  in  1903  came  Nor- 
mann  who  disclosed  the  application  of  nickel  catalyzer  to  the  hydro- 
genation  of  fixed  or  fatty  oils  or  the  production  of  stearin  from  olein. 
But  it  was  years  afterwards  before  the  idiosyncrasies  of  catalytic 
nickel  were  fully  understood  and  the  technical  difficulties  of  hydro- 
genation  were  surmounted  so  as  to  afford  eminently  practical  results. 

To-day  this  branch  of  the  oil  industry  is  growing  by  leaps  and 
bounds  and  its  advent  into  the  field  has  brought  a  flood  of  congratu- 
lations, protests  and  criticisms,  market  disturbances,  and  great  activity 
among  chemists  to  improve  the  catalytic  materials  and  processes  of 
treatment  involved. 

The  present  book  it  is  hoped  will  be  of  assistance  to  the  practical 
worker  as  well  as  to  the  student  of  oils  and  fats.  It  has  been  the  out- 
growth of  a  number  of  years  of  observation  and  experience  involving 
the  collection  of  a  considerable  amount  of  data  from  many  sources. 
An  attempt  was  made  by  the  author  to  present  the  matter  in  brief  form 
before  the  Society  of  Chemical  Industry  in  1912  and  the  present 
volume  is  based  on  the  general  plan  or  arrangement  of  material  adopted 
in  that  paper. 

Heretofore,  the  literature  on  hydrogenation  has  been  scattered 
through  many  periodicals  and  no  effort  has  been  made  to  collect  this 
material  and  arrange  it  in  book  form,  although  the  treatises  of  Hefter 
and  Ubbelohde  and  Goldschmidt  include  a  few  pages  on  the  conversion 
of  soft  fats  by  various  methods  to  stearic  acid  or  stearin;  but  such 
reviews  have  been  too  brief  to  afford  the  practical  operator  sufficient 
working  material. 

A  considerable  mass  of  data  including  practically  all  that  has  been 
advanced  on  the  subject  of  hydrogenation  of  fatty  oils  has  been  col- 
lected and  arranged  in  this  volume.  The  observations  and  opinions 
of  many  minds  have  been  brought  together.  Some  of  these  views 
obviously  are  sound,  others  are  open  to  grave  doubt  and  still  others 
are  of  a  contradictory  or  polemical  nature.  Whether  or  not  in  the 
treatment  of  this  material  to  carry  through  a  vein  of  critical  comment 
was  a  problem  which  confronted  the  author  and  the  conclusion  was 
reached  that  at  this  stage  of  a  young  art,  it  would  be  inadvisable  in 
general  to  do  more  than  array  the  multitude  of  processes,  formulae, 
proposals  and  opinions,  leaving  to  the  reader  the  selection  of  that 
which  should  prove  of  greatest  utility. 

A  few  years  hence  when  oil  hydrogenation  will  have  found  its 
measure  and  the  more  important  points  concerning  it  have  reached 


PREFACE  TO  THE  FIRST  EDITION  vii 

definite  settlement,  the  allotment  of  space  to  a  number  of  the  discus- 
sions appearing  on  the  following  pages  would  hardly  be  warranted,  but 
at  the  present  time  when  many  are  desirous  of  having  at  hand  a  treatise 
which  comprises  all  or  nearly  all  the  published  work  to  date,  containing 
though  it  does  a  considerable  divergency  of  opinion,  there  appears 
ample  justification  for  the  inclusion  of  material  which  later  may  be 
considered  superfluous. 

Frequent  reference  has  been  made  to  the  material  scattered  through 
the  literature  and  acknowledgment  is  rendered  to  these  sources  of 
information,  especially  to  the  Journal  of  the  Society  of  Chemical 
Industry  and  the  Seifenseider  Zeitung. 

C.  E. 

MONTCLAIR,  N.  J. 

June  15,  1914. 


CONTENTS 


PAGES 
CHAPTER  I. — METHODS  OF  HYDROGENATION 1-32 

Attempts  to  Hydrogenate  Oleic  Acid — A  Review  of  the  Art — 
Work  of  Lewkowitsch — Goldschmidt — de  Wilde  and  Reychler — 
Chlorination  of  Oils — Imbert,  Ziirrer — Tissier — Freundlich  and 
Rosauer — Varentrapp  Reaction — Schmidt  Zinc  Chloride  Process — 
Processes  Involving  the  Aid  of  Electricity — Magnier,  Bragnier  and 
Tissier,  Hemptinne,  Petersen,  Bohringer  and  Bruno  Waser — Hydro- 
genation  by  Catalytic  Action — Kolbe,  Sayteff,  Sabatier  and  Senderens 
— Nickel  Catalyzer — Leprince  and  Siveke  and  the  Normann  Patent — 
Hydrocarbon  Oils — Day — Oleic  Acid  Treated  in  the  Form  of  Vapor — 
Schwoerer,  Bedford — Erdmann  System — Vereinigte  Chemische  Werke 
A.G. — Kayser  Apparatus-^-Testrup  and  Wilbuschewitsch — Bedford 
and  Williams — Nickel  Oxide — Nickel  Carbonyl — Shukoff — Day, 
Phillips  and  Bulteel — Schlinck  Centrifugal  Apparatus — Ellis  System — 
Speed  of  Catalytic  Action — The  Treatment  of  Oleic  Acid — Connstein 
and  von  Schonthan,  Pfeilring  Reagent — De  Hemptinne. 

CHAPTER  II. — METHODS  OF  HYDROGENATION  (Continued) 33-49 

Utescher — Action  of  Light — Walter's  Method — Birkeland  and 
Devik — Brochet — de  Kadt — Markel  and  Crosfield — Temperature  of 
Hydrogenation — Caro — Fuchs — Nickel  Carbonyl,  Lessing — Kamps — 
Bremen-Besigheimer  Olfabriken — Scherieble — The  Calvert  System — 
Wilbuschewitsch  Apparatus — Wimmer  and  Higgins — Ellis — Bock. 

CHAPTER  III. — METHODS  OF  HYDROGENATION  (Continued) 50-107 

Early  Work  of  Bedford — Erdmann  and  Bedford — Badische  Co. — 
Voswinckel  Laboratory  Apparatus — Laboratory  Type  of  Hydro- 
genator  —  Dewar  and  Liebmann  —  Chisholm  Process  —  Kimura  — 
Rather  and  Reid — Hydrogenation  of  Ethylene — Asp  Bock — David 
Process  —  Adam  —  Griiner  —  Rontgen  Rays — Wielgolaski — Experi- 
ments by  Custis — Method  of  Charlton — Apparatus  of  Verona-Rinati 
— Colletas — Ellis — Humphreys'  Process — Method  of  Mandelstam — 
Moore  Process — Hendricks — Ney's  System — Maryott — De  Jahn — 
Methods  Employed  by  Calvert — Walter's  Magnetic  Method — Pictet 
— Birkeland — Devik — Utescher — Walker  Process — McElroy — Ellis — 
Reid  Laboratory  Apparatus — Higgins — Kalnin  and  Bergius — Barbe 
and  DePaoli — Laboratory  Method  of  Dubovitz — Normann's  Criti- 
cism— Robson — Method  of  Arnold — Hoehn  Process — Lane  System — 
Further  Details  of  De  Hemptinne's  Process — Solomonoff — Hardening 
by  Means  of  Ammonia  and  Amines — Herzmann — De  Conno — 
Hydrazine  Hydrate — Faciola — Mannino — Elaidin — Brochet's  Obser- 
vations— Morrill — Shuck  Deodorization  Method — Schrauth — Hig- 

ix 


x  CONTENTS 

PAGES 

gins'  Electrolytic  Process — van  Leent — Schicht  A.G.  and  Grim — 
Synthetic  Esters — Bedford — Morrell — Investigations  by  Author — 
Dreymann's  Esterification  Method — Use  of  Glycerine — Sugita — 
Ittner's  Process — Feld — Whitaker's  Method  for  Removing  Catalyzer 
— Hagemann  and  Baskerville — Maxted  and  Risdale — Higgins'  Cup 
Agitator — Hydrogenation  of  Resins — Moore,  Richter  and  Van  Arsdel 
— Hydrogenation  Curves — Effect  of  Temperature  and  Pressure — 
Percentage  of  Catalyzer — Effect  of  Agitation — Changes  in  Physical 
and  Chemical  Constants — Melting  Point — Titre — Halphen  Test — 
Miscellaneous  Publications  on  Hydrogenation — Lessing — Rivals — 
Jaubert — Ueno — Wilbuschewitsch — Schicht — Sjoquist — Siegmund — 
Hertzog  —  Fahrion  —  Redgrove  —  Klimont  —  Jobling  —  Bremen- 
Besigheimer  Olfabriken — Bergius — Ellis — Fabris — Shaw — Anderson 
— Robson — Schicht  A.G.  and  Griin — Kayser — Boehringer — Hydroil 
Co.,  Ltd. — Schmidt  and  Blankenhorn — Barnitz — Amburger — Uchida 
— Mock  and  Blum — Walker  Process. 

CHAPTER  IV. — CATALYZERS   AND   THEIR   ROLE   IN   HYDROGENATION 

PROCESSES.    THE  BASE  METALS  AS  CATALYZERS 108-117 

Nickel  Catalyzers — Preparation — Bodies  Acting  as  Poisons  for 
Catalytic  Nickel — Use  of  Nickel  by  Mond — Sabatier  and  Senderens 
— Behavior  of  Catalytic  Nickel — Senderens  and  Aboulenc — Nickel 
Obtained  by  Reducing  Various  Oxides — Classification  of  Catalyzers. 

CHAPTER  V. — THE  BASE  METALS  AS  CATALYZERS. 118-145 

Nickel  Oxide — Bedford  and  Williams— Erdmann — Sabatier 
and  Espil — Relative  Efficiency  of  Nickel  and  its  Oxide — Meigen  and 
Bartels — Kast — de  Kadt — Nickel  Soaps — Hausmann — Wimmer  and 
Higgins — Nickel  Formate — Crosfield — Kayser — Wilbuschewitsch  — 
Frank — Eldred — Miiller — Nickel  (Hypophosphite — Bremen-Besighei- 
mer  Olfabriken — Flaky  Nickel — Hagemann  and  Baskerville — Boberg 
— Boron  as  a  Catalyzer — Hildesheimer — Continuous  Process  for  the 
Reduction  of  Nickel  Oxide. 

CHAPTER  VI. — THE  BASE  METALS  AS  CATALYZERS  (Continued) 146-171 

Dewar  and  Liebmann — Catalyzer  from  Nickel  Hydrate — Kayser 
— Lubeck  and  Payet — Silicon  Monoxide — Valuable  Qualities  of  Char- 
coal— Fresenius — Author's  Process — Ellis  and  McElroy— Ittner's 
Charcoal  Catalyzer — Tamari — Valpy  and  Lucas — Effect  of  Promoters 
— Badische  Co. — Crossley — Hehner — Bosch,  Mittasch  and  Schneider 
— Kayser's  Reduction  Apparatus — Morey  and  Craine  Reducer — 
Morey's  Process — Burchenal  Catalyzer — Pyrophoric  Catalyzers  — 
Oswald  and  Doering— Colloidal  Nickel — Sulzburger— Catalyzer  Poi- 
sons— Sabatier  and  Espil — Effect  of  Sulphur  and  Chlorine — Potas- 
sium Cyanide — Peters — Author's  Process  for  Removing  Catalyzer 
Poisons— Ellis  and  Wells— Treatment  of  Fish  Oils— Effect  of  Sul- 
phates— Arsenic — Crossley — Hehner — Kelber — Carbon  Bisulphide — 
Moore,  Richter  and  Van  Arsdel — Bancroft — Carbon  Monoxide — 
Maxted — Pierron  Catalyzer — Hagemann  and  Baskerville  Nickel 


CONTENTS 


XI 


Sheet  Catalyzer — Elworthy — Karplus — Nitrogen  Ges.  m.b.  H.— 
Hamburger's  Experiments — Reduction  of  Nitro  Compounds — Mag- 
netic Separation — Walter's  Process — Reynolds'  Method — Ellis  Pro- 
cess— Leimdorfer — Ipatiew  and  Zvjagin — Rolla — Naamlooze  Ven- 
nootschap — Soc.  Industrielle — Lane's  Reduction  Apparatus — Edison 
Reduction  Process. 

CHAPTER  VII.— THE  BASE  METALS  AS  CATALYZERS  (Continued).. 
Wesson's  Catalyzer — Making  Nickel  Hydrate — Woodruff — 
Badische  Co. — Permutit — Richardson  Electrical  Method — Author's 
Methods — Olverwertung  G.  m.  b.  H. — Electrolytic  Deposition  of 
Catalytic  Nickel — Use  of  Silicon  Tetrafluoride — Sabatier  and  Espil — 
Bacon  and  Nicolet  Catalyzer — Wells  Catalytic  Material — Sulzburger 
— Method  of  Using  Nickel  Carbonyl — Nickel  Silicate — Byrom — 
Sulzburger's  Silica  Catalyzer — Nickel  Borate — Schoenfeld — Criti- 
cisms of  Erdmann  and  Rack — Normann  on  Nickel  Borate — C.  and  G. 
Muller  Speisefettfabrik  —  Bremen-Besigheimer  Olfabriken — Nickel 
Benzoate — Nickel  Boride  and  Carbide — Use  of  Paraffin  Wax — Reduc- 
tion of  Nickel  Hydrate — Kelber — Fuchs — Nickel  Carbonate — Morri- 
son's Method  of  Recovering  Catalyzer — Haas — Filtration  of  Colloidal 
Nickel — Proposed  Use  of  Hydrated  Silicic  Acid — Bosch,  Mittasch  and 
Schneider — Organic  Salts  of  Nickel — Snelling — Copper  Formate — 
Spieler — Nickel  Formate — Decomposition  of  Nickel  Formate — Use  of 
Formic  Acid — Higgins'  Process — Valpy  and  Lucas — Nickel  Acetate, 
Oxalate  and  Tartrate — Copper  Catalyzer  for  Reducing  Nitro  Com- 
pounds— Nickel  Oleate — Richardson  Process — Hausmann — Thieme 
and  Geitel— Author's  Method  of  Using  Nickel  Oleate— Thermal 
Decomposition — Colloidal  Nickel — Wimmer  and  Higgins — Reduction 
in  Oil — Nickel  Acetate — Soc.  de.  Stearinerie  et  Savonnerie. 

CHAPTER  VIII.— THE  BASE  METALS  AS  CATALYZERS  (Continued) 

Notes  on  Nickel  Oxide  Catalyzers — Bedford  and  Erdmann — 
Normann  on  the  Production  of  Metallic  Nickel — Criticism  by  Nor- 
mann and  Pungs — Determination  of  Electrical  Conductivity — 
Analytical  Determination  of  Free  Nickel — Nickel  Carbonyl  Test — 
Metallic  Nickel  vs.  Nickel  Oxide — Controversy  between  Erdmann  and 
Normann — Olwerke  Germania — Hoyer — Paal  and  Brunjes — Robson 
— Catalyzer  Employed  by  Suzuki-Shoten  Co. — Bedford,  Williams, 
Erdmann  and  Hydroil  Company,  Ltd.,  Ellis  Semi-Reduced  Hydro- 
genation  Catalyzer — Boyce's  Nickel  Black — Boehringer — Meigen 
Assertions — Frerichs'  Criticism  of  Erdmann's  Observations — Further 
Work  of  Normann — Lever  Bros. — Erdmann  and  Bedford — Hydro- 
genation  by  Means  of  Nickel  Oxide  and  Metallic  Nickel — Agde — 
Experiments  in  Support  of  Erdmann's  Contentions — Effect  of  Mois- 
ture in  Catalyzer — Reduction  of  Nickel  Compounds  in  Saturated 
Bodies — Effect  of  Sulphuric  Acid — Siegmund  and  Suida — Experi- 
ments with  Nickel  Oxide  and  Linseed  Oil — Sesame  and  Cottonseed 
Oil — Nickel  Formate — Character  of  the  Nickel  Catalyzer  Obtained 
from  Different  Sources. 


PAGES 


172-198 


199-228 


xii  CONTENTS 

PAGES 
CHAPTER  IX.— NICKEL  CARBONYL 229-241 

Discovery  of  Nickel  Carbonyl  by  Mond  (Properties) — Martha — 
Berthelot — Manufacture  on  the  Large  Scale — Fierz — Langer — Dewar 
— Catalytic  Action  of  Nickel  Derived  from  Nickel  Carbonyl — 
Author's  Method— Lessing  Process — George  Schicht,  A.G. — Coleman. 

CHAPTER  X. — THE  RARE  METALS  AS  CATALYZERS 242-264 

Palladium — Fokin's  Experiments — The  Work  of  Paal — Colloidal 
Palladium — Platinum  and  Palladium  Chloride — Skita — Protective 
Colloids — Bredig — Meyer  on  the  Use  of  Palladium  Compounds — 
Karl — Paal  and  Windisch — Stark — Osmium  Oxides — Lehmann — 
Paal  and  Hartmann — Thron — Porter — de  Montlaur — Schick — Perl 
— Efrem — Munroe — Oil  Colloids,  Paal  and  Amberger — Hydrogena- 
tion  of  Olive  Oil — Cerium  Catalyst — Osmium  and  Ruthenium  Com- 
pounds on  Carriers — Use  of  Coloidal  Palladium  by  Albright — 
Badische  Co. — Fahrion — Cost  of  Palladium  Catalyzer — Skita's 
Observations  on  the  Rate  of  Hydrogenation — Sabatier — Mailhe — 
Neumann — Niedenfuhr — Fokin's  Claims — Classen — Groh — Zelinsky 
— Dehydrogenation — Normann  and  Schick  on  Osmium — Platinum 
on  Charcoal  Mannich — Platinum  on  Coke  Verona-Rinati — Author's 
Use  of  Charcoal  and  Other  Forms  of  Carbon — Mannich  and  Thiele — 
Hydrogenation  of  Peanut  Oil — Propylene  Heinemann — Boseken  and 
Hofstede — Mittasch,  Schneider  and  Morawitz — Amburger's  Organo 
Salts — Zeolites — Silicic  Acid — Schwerin — Schwarcman  Catalyzer — 
Palladium  Catalyzer  of  Sulzburger — Killing. 

CHAPTER  XI. — THE  OCCLUSION  OF  HYDROGEN  AND  THE  MECHANISM 

OF  HYDROGEN  ADDITION     265-280 

Absorption  of  Hydrogen  by  Various  Metals — Sieverts  and 
Krumhaar  —  Dehydrogenation  —  Padoa  and  Fabris  —  Palladium 
Hydrides — Wieland — Nickel  Hydrides — Sabatier — Mayer  and  Alt- 
mayer— Phenomena  of  Adsorption — McBain — Reducing  Power  of 
Hydrogen — Tomassi — Occlusion  of  Hydrogen  by  Charcoal — Titoff — 
Firth — Electrolytic  Hydrogen — Fokin — Sieverts,  Jurisch  and  Metz 
— Smith  and  Martin — Jurisch — Joukoff — Korevaar — Pomilio — Elec- 
trolytic Reduction  of  Unsaturated  Acids — Comparative  Ease  of 
Hydrogenation — Erucic,  Ricinoleic  and  Linolenic  Acids — Boseken 
and  Bilheimer. 

CHAPTER  XII. — THE    ANALYTICAL    CONSTANTS    OF    HYDROCIZNATED 

OILS 281-318 

Changes  in  Specific  Gravity,  Melting  Point  and  Iodine  Number 
— Normann  and  Hugel — Index  of  Refraction — Saponification  Value — 
Cholesterol  and  Phytosterol — Bomer — Willstatter  and  Mayer — The 
Unsaponifiable  Constituents  of  Hydrogenated  Oils — Marcusson  and 
Meyerheim — Hardened  Castor  Oil — Garth — Boudouin  Reaction, 
Halphen  and  Becchi  Tests — Erucic  Acids — Lewkowitsch — Majima 
and  Okada — Hardened  Peanut  Oil — Kreiss  and  Roth — Observations 
of  Knapp — The  Investigations  of  Bomer — Leimdorfer — Color  Reac- 


CONTENTS  xiii 

PAGES 

tions  of  Hydrogenated  Fish  Oils — Grimme — Codex  Alimentarius 
Austriacus  —  Aufrecht  —  Tests  for  Nickel  —  Dimethylglyoxime — 
Tchugaeff  —  Fortini  —  Benzildioxime  —  Atack  —  Colorimetric  Met- 
hod— Lindt — The  "  Hydrogen  Value  " — Fokin — Seidenberg  Method 
of  Detecting  Hardened  Oil  in  Butter — Researches  of  Twitchell — 
Fatty  Acids  in  Fish  Oil — Crossley — Passmore — Hydrogenation  of 
Fatty  Acids — Tortelli  and  Joffe  Reaction — Davidsohn — Tsujimoto — 
Fryer  and  Weston — Detection  of  Hydrogenated  Oils — Pickering's 
Method — Sandelin — Constants  of  Whale  Oil — Halphen  Test — Leh- 
mann — Peanut,  Sesame  and  Cottonseed  Oil — Kelber  and  Rhein- 
heimer — Iodine  Numbers — Nickel  Content  of  Hardened  Oil — 
Lehmann's  Methods — Frail's  Test — Ash  of  Hardened  Oil — Schoen- 
feld — Effect  of  Hydrogen  on  Oil  Containing  Dissolved  Nickel — 
Albright's  Method  for  Determining  the  Hydrogen  Number — Hyland 
and  Lloyd — Partially  Hydrogenated  Oils — Detection  of  Phytosterol — 
Kerr — Prescher — Detection  of  Hardened  Oil  in  Lard — Sprinkmeyer 
and  Diedrichs — Mannich  and  Thiele — Completely  Hydrogenated 
Fats — Marcusson  and  Meyerheim — Effect  of  Hydrogenation  on 
Cholesterol  and  Phytosterol — Marcusson  and  Huber — Octodecyl 
Alcohol  —  Chrysalis  Oil  —  Tsujimoto  —  Spinacene  —  Chapman  — 
Normann  and  Hugel — Glycerine  Content  of  Hardened  Fats — Jurgens 
and  Meigen— Hydroxy  Fatty  Acid — Svendsen — Hardened  Whale  Oil 
— Bosshard  and  Fischli — Anderson  and  Katz — Use  of  Sodium  Oleate — 
Biazzo  and  Vigdorcik — Determination  of  Rape  Oil — Kelber — Removal 
of  Halogen — Lowenstein — Halphen  Test — Amberger's  Method  of 
Detecting  Hydrogenated  Oils — Knorr — Testing  for  Sulphur. 

CHAPTER  XIII.— EDIBLE  HYDROGENATED  OILS  319-337 

Lard  Compound  Manufacture — Advantages  in  the  Use  of  Hydro- 
genated Oil — Apparatus  Employed  in  Mixing  Hydrogenated  Oil  with 
Other  Oils-  -Joslin — Lecithin — Riedel — Brebesol — Edibility  of  Hydro- 
genated Oils — Bomer — Effect  of  Nickel  in  the  Hardened  Product — 
Normann  and  Hugel — Meyerheim — Hardened  Whale  Oil  in  Fats 
Intended  for  Edible  Purposes — Bohm — Lieber  and  Keutgen — Offer- 
dahl  —  Miscellaneous  Hardened  Oil  Products  —  Oleomargarine  — 
Deveaux — Hydrogenated  Soya  Bean  Oil — Ellis-Boyce  Process — Palm 
Oil  —  Wilbuschewitsch  —  Erlandsen  —  Fridricia — Elgstrom — Diges- 
tibility of  Hydrogenated  Whale  Oil. 

CHAPTER  XIV.— EDIBLE    HYDROGENATED    OILS    (Continued) 338-357 

Wesson's  Observations — Gill — Klimont  and  Mayer — Bontoux — 
Bergius — Pekelharing  and  Schut — Feeding  Experiments  with  Hydro- 
genated Oils— Thorns  and  Muller — Holmes  and  Lang — Estabrook's 
Product — Kohman,  Godfrey  and  Ashe,  and  the  Use  of  Hardened  Oil 
in  Bread  Making — Powdered  Hydrogenated  Oil — Atkinson — Hoi- 
brook — Baking  Powder  Containing  Hardened  Oil — Burchenal's 
Method  of  Producing  Lard-like  Fats — Walker  Method — Lehmann — 
Further  Notes  on  the  Presence  of  Nickel  in  Hardened  Oil — Vuk — 
Gheorghiu — Nickel  Free  Fat — Increasing  the  Glycerine  Content  of 


xiv  CONTENTS 

PAGES 

Oils — Schweitzer — Corn  Oil — Sayre — Crisco  Plant — Joslin  Purifica- 
tion Method — Wilbuschewitsch — Thompson  on  Linseed,  Soya  Bean, 
Peanut,  Cottonseed  and  Fish  Oils — Salad  Oil — Lowenstein — Water- 
holding  Capacity  of  Hydrogenated  Oils — Brauer — Nutritive  Value 
of  Butter  Substitute  Containing  Hydrogenated  Oil — Halliburton  and 
Drummond — Clayton — Pickard  on  Oleomargarine — Keebler — Koh- 
man,  Godfrey  &  Asche — Vegetole — Armour — Bernegau — Freres — 
Lecithin — Daughters. 

CHAPTER  XV. — USES  OF  HYDROGENATED  OILS  AND  THEIR  UTILIZA- 
TION IN  SOAP  MAKING 358-389 

Applications  of  Hardened  Oils — Fish  Oils — Tsujimoto — Whale 
Oil — Garth — Products  of  the  Germania  Olwerke — The  Investi- 
gations of  Schaal  on  the  Uses  of  Hydrogenated  Oils  in  the  Manu- 
facture of  Soap — Bergo — Limitations  on  the  Uses  of  Hydrogenated 
Oil— Hauser— Ribot— Weber— Muller  —  Fatty  Acids  of  Hydro- 
genated Oils  —  Hajek  —  Garth  —  Tariff  Ratings  —  Bohm  —  Cru- 
tolin  Soaps — Hydrogenated  Linseed  Oil  and  Soaps  Made  from  It — 
Linolith. 

CHAPTER  XVI.— USES  OF  HYDROGENATED  OILS  AND  PROPERTIES  OF 

CERTAIN  HARDENED  PRODUCTS  . 390-411 

Ittner — Fish  and  Whale  Oil — Hydrogenated  Torpedo  Liver  Oil — 
White — Tsujimoto — Shark  Liver  Oil — Calamary  Oil — Ueno — Schuck 
— Knorre — Results  of  Using  Fish  Oil  in  Making  Soap — Properties  of 
Fatty  Acids  of  Hardened  Fish  and  Whale  Oil — Polymerized  and 
Hydrogenated  Oils — Dubovitz — Production  of  Stearine — Bontoux — 
Fat  Splitting — Soap  Formulas — Schaal — Davidsohn — Demand  for 
Hardened  Oil — Schrauth — Schrapinger — Hardened  Chinese  Wood 
Oil — Levinstein — Sulphonated  Oils — Karite  Butter — Aoura— sHeim 
— Hebert — Padoa  and  Dalla — Schmitz — Lubricants  Containing 
Hardened  Oil — Krist — Brooks'  Process  of  Hydrogenating  Rosin — • 
Reuter — Hardened  Oil  in  Paints — Cordes — Electrical  Condensers — 
Hardened  Oil  in  Pharmacy — Lackey  and  Sayre — Hardened  Corn  Oil 
— Fox — Mixtures  of  Hardened  Oil  and  Non-fatty  Material — Ellis — 
Sadtler. 

CHAPTER  XVII.— HYDROGENATION  PRACTICE      412-417 

Catalyzer  Apparatus — Hydrogenation  Plant — Precautions  to  be 
Observed — Simple  Type  of  Converter — Temperature  Control — 
Filtration. 

CHAPTER  XVIII. — THE  HYDROGENATION  OF  PETROLEUM 418-438 

Experiments  of  Winckler — California  Petroleum — Nickel  Oxide 
and  Other  Catalyzers — Snelling — Colloidal  Carbon  and  Nickel — 
Other  Methods  of  Using  Nickel  Catalyzer— Planes,  Ltd. — White— 
Evans — Porges  and  Stransky — Oxides  of  Lead  and  Nickel — Chichi- 
babin — Heyl  and  Baker — Sobering — Franke — Iron,  Nickel,  Chro- 
mium and  Platinum — Holcgreber — Ellis  and  Wells — Deodorizing 


CONTENTS  xv 

PAGES 

Gasoline  by  Hydrogenation — Tinkler  and  Challenger — Danckwardt — 
Testelin  and  Renard — Moeller  and  Woltereck — Process  of  Badische 
Co. — Brooks,  Bacon,  Padget  and  Humphrey — Reduction  in  Olefine 
Content  of  Cracked  Gasoline — Humphreys — Process  of  Porges, 
Stransky  and  Strache — Continental  Caoutchouc  and  Gutta  Percha 
Co. — Ultraviolet  Rays — Experiments  of  Brooks — Valpy  and  Lucas 
Process — Catalyst  for  Cracking  Petroleum  Oil — Sabatier  and  Mailhe 
— Treatment  of  Gasoline  with  Nickel — The  Hall  Process — Use  of 
Nickel  Rods — Water  as  a  Hydrogenating  Agent — Lamplough  Process 
— Higgins  and  Preston — Automobile  Engine  Fuel — Method  of  Low 
—Wells  Process  Using  Molten  Lead — Nickel  Plated  Metal— Con- 
clusions of  Whitaker  and  Leslie — Bergius  High-pressure  Process — 
Billwiller— Standard  Oil  Company — Use  of  Metal  Plates  as  Catalytic 
Surfaces— Day's  Sulphur  Process — Rostin  and  Forwood  Method — 
Use  of  Hydrogen  Sulphate — Simplex  Refining  Company — Brown's 
Apparatus — Downing  and  Pohlman — Davidson  and  Ford — Cherry's 
Electric  Process — Hirt — Coast — Thompson's  Catalyzer — Organic 
Salts  of  Nickel — Experiments  of  Cross — Rittman  and  Jolicard — 
— Zerning — Cracking  Tars  and  Oils. 

CHAPTER  XIX.— THE  HYDROGEN  PROBLEM  IN  OIL-HARDENING 440-443 

Hydrogen  Requirements  of  Oils — Sources  of  Hydrogen — ^By- 
Product  Hydrogen — Water  Gas — Coke  Oven  Gas — Walter's  Con- 
clusions. 

CHAPTER  XX. — WATER  GAS  AS  A  SOURCE  OF  HYDROGEN  AND  THE 

REPLACEMENT  OP  CARBON  MONOXIDE  BY  HYDROGEN 444-459 

Reaction  of  Carbon  Monoxide  with  Lime  in  the  Presence  of 
Steam — Engles— Tessie  du  Motay — Chem.  Fabrik  Griesheim 
Elektron — Merz  and  Weith — Jermanowski — Hembert  and  Henry 
Process — Mond  and  Langer — Elworthy — Ellis  and  Eldred — Dief- 
fenbach  and  Moldenhauer — Naher  and  Miiller — Pullman — Miscel- 
laneous Processes  Involving  Interaction  between  Carbon  Monoxide 
and  Steam— Bosch  and  Wild— Use  of  Nickel  or  Cobalt  Catalyzer- 
Other  Methods  Employed  by  Badische  Co. — Ellis  Process — Griesheim 
Elektron — Vignon  Method — Buchanan  and  Maxted — Use  of  Alkali 
Ferrite — Siedler  and  Henke  Process. 

CHAPTER  XXI. — LIQUEFACTION    AND    OTHER    METHODS    FOR    THE 

REMOVAL  OF  CARBON  MONOXIDE 460-470 

Principle  of  Liquefaction  by  Compression — Hildebrandt — Linde 
System — Liquefaction  Apparatus — Claude — Jouve  and  Gautier — 
— Vignon — Absorption  of  Carbon  Monoxide  by  Chemical  Agents — 
Frank  Process — Claude  Apparatus — Method  of  Separating  Hydro- 
gen— Badische  Co. — Mewes. 

CHAPTER  XXII. — HYDROGEN   BY   THE   DECOMPOSITION  OP   HYDRO- 
CARBONS    471-484 

Effect  of  Heat  on  Hydrocarbons — Acetylene — Pictet — Car- 
bonium  Company — Wachtolf — Geisenberger — Decomposition  of  Oils 


xvi  CONTENTS 

«  * 

PAGES 

— Rincker  and  Wolter  System — Oechclhauser — Pictet's  Oil  Process — 
Decomposition  of  Natural  Gas— Frank's  Process — Rose— Herman— 
Mittasch  and  Schneider — Use  of  Nickel— Brownlee  and  Uhlinger — 
Production  of  Hydrogen  and  Carbon  Black — Bacon,  Brooks  and 
Clark  —  Ellis  Process  —  Modified  Rincker- Wolter  Process  —  Barth 
System — Snelling  Method — Brunner's  Apparatus. 

CHAPTER  XXIII. — HYDROGEN  BY  THE  ACTION  OF  STEAM  ON  HEATED 

METALS 485-514 

Reaction  of  Steam  with  Iron — Giffard — Lewes  Process — Dellwik- 
Fleischer  System — Lane  Process — Processes  Devised  by  Messer- 
schmitt — Elworthy — Internationale  Wasserstoff-Aktien-Gesellschaft 
— Strache  System — Dieffenbach  and  Moldenhauer — Badische  Co. — 
Belou— Vignon's  Apparatus — Effect  of  Passing  Steam  through 
Molten  Metal— Gerhartz — Jaubert  Method — Acceleration  of  the 
Reaction  by  Catalytic  Agents — Saubermann — Gautier  and  Claus- 
mann — Messerschmitt  Process  and  Improved  Types  of  Apparatus — 
Naher  and  Noding — Spitzer  Generator — Schaefer  Producer--The 
Dempster  System — Triple  Furnace  of  Bosch — Dicke — Maxted  and 
Ridsdale  —  Pintsch  —  Jaubert  —  Hooton  —  Tully  Process  —  Mul- 
tiple Retort  System  Improved  Equipment  Company — Bergius  and 
Posen — Process  of  Berlin  Anhaltische  Masch.  A.G. 

CHAPTER  XXIV.— ACTION  OF  ACIDS  ON  METALS 515-518 

Cost  of  Generation — By-products — Barton  System — Method 
Used  by  Pratis  and  Marengo — Proposal  ot  Bruno — Stuart  Scrap 
Iron  Method— Becquevort  and  Deguide — Curran. 

CHAPTER  XXV. — MISCELLANEOUS    METHODS    OF    HYDROGEN    GEN- 
ERATION      519-535 

Foesterling  and  Philipp— Brindley — Calcium  Hydride — Jaubert 
— Bamberger,  Bock  and  Wanz — Reaction  between  Zinc  Dust  and 
Calcium  Hydrate — Schwartz — The  Hydrogenit  Process — Jaubert — 
The  Silicol  Process — The  Hydrik  Process — Mauricheau-Beaupre — 
Chem.  Fab.  Greisheim  Elektron— Uyeno— Majert  and  Richter  Sys- 
tem— The  Lahousse  Barium  Sulphide  Process — The  Bergius  High- 
pressure  System — Sabatier  Process — Baillio — De  la  Fresnaye  and 
Suchy — Kessener — Snelling  Diffusion  Process — Wtissow — The  Curme 
Method— Scholl— Oyobigawa— Quentin  and  Gullien— Helbig — Acti- 
vation of  Aluminum — Hamlin — Hydrogen  for  Military  Balloons — 
Fourniols — Barnitz — Seeker — Bontoux — Sander — Redgrove — Ardery 
— Hydrogen  Gas  in  Aeronautics — Crossley — Kausch — Process  of 
Teissier  and  Chaillaux. 

CHAPTER  XXVI.— HYDROGEN   AND   OXYGEN   BY   ELECTROLYSIS   OF 

WATER 536-589 

Principles  Involved  in  Generating  Hydrogen  and  Oxygen  by 
Electrolysis — Work  of  D'Arsonval,  Latchinoff  and  Renard — Schmidt 
Multiple-cell  Apparatus— Shriver  Oxy-hydrogen  Generator— Schoop 


CONTENTS 


xvn 


System — Principle  of  Garuti  Generator — Types  of  Garuti  Apparatus 
— Siemens  and  Obach  Cell — Fischer,  Luening  and  Collins — The 
Schuckert  System — Principle  of  the  Schuckert  Cell — Installation  and 
Operating  Features — Rotary  Apparatus  Devised  by  Aigner — Cowper 
— Coles — Miscellaneous  Forms  of  the  Multiple-cell  Generator — Tom- 
masini  Cell — Vareille  Apparatus — The  Burdett  System — The  System 
of  the  International  Oxygen  Co. — Bettendorf  Plant — National 
Ox-hydric  Company — Modified  Apparatus  of  International  Oxygen 
Co. — Multiple  Type — Sectional  Type — Shriver  Apparatus — Oerlikon 
— Schmidt  Electrolyzer — Dohmen — Levin  Generator — Electrolabs 
System — Compact  Sectional  Form  of  Electrolyzer — Griffin's  Appara- 
tus— Kato — Halter — The  Davis-Bournonville  Co.  Electrolyzer — 
Swartley  Separator — Method  of  Assembling — System  of  Automatic 
Control  of  Davis-Bournonville  Co. — Jones  Cell — Shaw — Hepburn — 
Frazer  Generator — Jaubert — Mueller  and  Rowlands. 


PAGES 


CHAPTER  XXVII. — PRECAUTIONS  IN  HANDLING  HYDROGEN. 
DEVICES.     PURIFICATION  OF  GAS  . 


SAFETY 


Davy  Wire  Gauze— Glass  Wool— Boy  nton's  Device— Steel  Wool 
— Ohmann — Explosions  When  Compressing — Bramkamp — Lelarge — 
Summary  of  Methods  of  Making  and  Handling  Hydrogen — Purifica- 
tion of  Hydrogen — Badische  Co. — Renard — Wenzki — Rabenalt — 
Knowles  System — Frank  Process — Pressure  Purification  Method  of 
Bosch  and  Wild — Badische  Co. — Soc.  L'Air  Liquide — Electrically- 
heated  Apparatus  of  Knowles — Siemens  and  Halske — Removal  of 
Oxygen — Ueno  and  Kimura — Use  of  High  Pressure  Apparatus — Pier— 
Effects  of  the  Presence  of  Hydrogen  in  Electrolytic  Oxygen — Bureau  of 
Mines— California  Commission-  -Hydrogen  with  Small  Percentages  of 
Oxygen,  a  Comparatively  Non-hazardous  Product — Wohler  Regula- 
tions in  Germany — Hammond's  Apparatus  to  Prevent  Polarity  Re- 
versal— The  Underwriters  Laboratories — Tentative  Standards  for 
Oxygen  and  Hydrogen — Oil  Hardening  Tank  Explosion. 


APPENDIX   A ; . 

Hydrogenated  Oil  Patent  Litigation, 
tion  of  Olwerke  Germania. 


Normann  Patent — Asser- 


590-603 


605-629 


APPENDIX  B 630-707 

Edible  Hydrogenated  Fats.  Patent  Litigation.  Crisco  and 
Kream-Krisp.  Early  History  of  Hydrogenation — Crosfield — Kayser 
— Burchenal — Proctor  and  Gamble — Berlin  Mills  Co. — Constitution 
of  Hydrogenated  Oils — Decision  of  Judge  Hand — Comments  on  the 
Crisco  Case. 

INDEX.  711-767 


THE  HYDROGEN ATION  OF  OILS 


CHAPTER  I 
METHODS   OF   HYDROGENATION 

FOR  years  the  dream  of  the  oil  chemist  was  to  find  a  solution  to  the 
problem  of  converting  oleic  acid  into  stearic  acid,  or  olein  into  stearin, 
simply  by  the  addition  of  hydrogen,  so  as  to  make  valuable  hard  fats 
from  relatively  cheap  raw  material.  Superficially  the  problem  looked 
simple.  Oleic  acid  is  the  next  door  neighbor  of  stearic  acid,  apparently 
differing  only  in  having  a  little  less  hydrogen  than  stearic  acid  has  in 
its  constitution.  Only  a  trifling  amount  of  hydrogen,  less  than  one 
per  cent,  is  required  to  transform  oleic  into  stearic  acid. 

But  the  problem  was  far  from  simple  as  oleic  acid  stubbornly  resisted 
the  invasion  of  hydrogen  into  its  structure  to  any  material  extent  under 
the  earlier  methods  of  hydrogen  addition,  and  not  until  recent  years, 
with  the  discovery  of  effective  hydrogen  carriers  or  catalyzers,  has  it 
become  possible  to  bring  about  this  conversion  economically  with  large 
yields  so  as  to  warrant  commercial  exploitation  in  an  extensive  way. 

Now  the  problem  is  solved,  and  in  different  parts  of  the  globe  dozens 
of  plants  turning  out  daily  enormous  quantities  of  "  hardened  oil  "  pre- 
pared by  the  treatment  of  vegetable  or  other  oil  with  hydrogen  have 
been  established.*  So  eagerly  has  the  oil  handling  world  lent  itself  to 
the  idea  that  already  the  stearin  market  has  lost  its  firmness  and  much 
speculation  is  rampant  as  to  the  nature  of  price  readjustments  which 
perhaps  are  on  the  way.  Unquestionably  hydrogenated  or  hardened 
oil  has  taken  its  place  in  the  oil  market  as  a  staple  product. 

A  REVIEW  OF  THE  ART.ft 

Many  attempts  to  hydrogenate  oleic  acid  have  been  made.  Re- 
viewing this  subject  in  1897  §  Lewkowitsch  refers  to  the  ease  with 

*  A  list  of  over  twenty  firms  in  different  parts  of  the  world  having  plants  for 
hardening  oils  is  found  in  Seifensieder  Zeitung,  1914,  349. 

t  See  Ellis,  J.  S.  C.  I.,  1912,  1155;  J.  Ind.  Eng.  Chem.,  1913,  95;  The  American 
Perfumer,  1913. 

t  The  production  of  stearic  acid  and  other  acids  or  products  of  high  melting  point 
from  oleic  acid  is  discussed  by  Hefter,  Technologic  der  Fette  und  Ole,  Vol.  Ill, 
795  and  994;  also  by  Ubbelohde  und  Goldschmidt,  Handbuch  der  Chemie  und 
Technologic  der  Ole  und  Fette,  Vol.  Ill,  152. 

§  J.  S.  C.  I.,  389  (1897). 

1 


2  THE  HYDROGENATION  OF  OILS 

which  the  lower  members  of  the  oleic  series  are  converted  into  satu- 
rated acids  and  states  that  "  oleic  acid  itself  resists  all  attempts  at 
hydrogenization,"  further  remarking  that  he  had  "  carried  out  a  large 
number  of  experiments  in  this  direction  under  most  varied  conditions, 
but  hitherto  all  of  these  gave  negative  results." 

Prior  to  this,  however,  Goldschmidt,  in  1875,*  had  reduced  oleic 
acid  by  means  of  hydriodic  acid  and  amorphous  phosphorus  at 
200°  to  210°  C.  This  presumably  led  to  the  attempted  commercial 
development  of  a  process  by  de  Wilde  and  Reychlerf  involving  heating 
oleic  acid  to  280°  C.  with  1  per  cent  of  iodine,  adding  and  melting 
therein  a  certain  quantity  of  tallow  soap,  and  then  boiling  with  acidu- 
lated water.  The  product  was  then  distilled  and  the  iodine,  in  part, 
recovered  from  the  pitch.  The  yield  of  stearic  acid  or  saturated  fat 
is  stated  to  be  approximately  70  per  cent  of  the  theoretical.  Only 
about  two-thirds  of  the  iodine  could  be  recovered  so  the  process  appar- 
ently did  not  find  technical  use. if  Should  the  much  lauded  method 
of  treating  kelp,  primarily  for  obtaining  potash  salts,  come  into  use,  a 
cheap  supply  of  iodine  would  be  available  which  might  then  make  the 
Wilde  and  Reychler  process  of  some  technical  interest. 

Chlorine  in  lieu  of  iodine  has  been  tried,  but  great  difficulty  has  been 
experienced  in  securing  an  autoclave  of  resistant  material.  Imbert  § 
recommends  using  quantities  of  chlorine  and  alkali  exactly  calculated 
on  the  iodine  number  of  the  fatty  acid  and  operating  at  a  temperature 
of  120°  to  150°  C,  and  a  pressure  of  about  five  atmospheres  for  a  period 
of  six  hours. 

Zurrer  ||  chlorinates  the  fatty  acid  and  then  heats  with  water  in  the 
presence  of  a  finely-divided  metal,  as  zinc  or  iron.  Lewkowitsch  alleges 
that  the  treatment  of  monochlor-stearic  acid  in  this  manner  causes  a 
reversion  to  oleic  acid. 

Tissier,  in  1897, 1f  lays  claim  to  a  process  for  the  reduction  of  oleic 
acid  by  nascent  hydrogen.  Powdered  metallic  zinc  is  placed  in  an  auto- 
clave, water  and  the  fatty  material  containing  olein  being  introduced, 
and  treated  under  pressure. 

Under  the  circumstances  the  glyceride  is  hydrolyzed  to  fatty  acid 
and  glycerine,  and  according  to  Tissier  nascent  hydrogen  is  evolved  by 

*  Sitz.  b.  d.  Wiener  Akad.  d.  Wiss.,  72,  366. 
t  Bull.  Soc.  Chim.  [3],  1,  295  (1889). 
j  Chem.  Ztg.,  1889,  595. 

§  U.  S.  Patent  No.  901,905,  October  20,  1908;  see  also  Bull.  Soc.  Chim.,  1899, 
695,  707. 

II   German  Patent  No.  62,407,  August  8,  1891. 
1[  French  Patent  No.  263,158,  January  16,  1897. 


METHODS  OF  HYDROGENATION  3 

virtue  of  the  finely-divided  metal  and  reduces  the  oleic  to  stearic  acid. 
Freundlich  and  Rosauer  *  claim  the  Tissier  process  to  be  inoperative. 

The  conversion  of  oleic  acid  into  palmitic  and  acetic  acids  by  means 
of  caustic  potash  in  accordance  with  the  Varentrapp  reaction  j  has  not 
proved  to  be  of  much  commercial  significance,  although  it  appears 
that  certain  firms  have  been  making  use  of  the  process  in  a  limited  way. 

The  Schmidt  zinc  chloride  process^  involves  heating  oleic  acid  and 
zinc  chloride  at  exactly  185°  C.  while  interaction  is  taking  place. 
"  Deviation  from  this  point  leads  to  an  increase  of  liquid  substance. 
Unfortunately  the  solid  candle  material  must  be  distilled  and  the  con- 
siderable proportion  of  0-hydroxy-stearic  acid  (melting  point  82°  C.) 
in  the  crude  product  is  seriously  diminished  by  the  partial  conversion 
of  this  acid  into  oleic  and  iso-oleic  acids.  Thus,  from  a  candle-maker's 
point  of  view,  a  substance  of  high  melting  point  is  rendered  practically 
valueless.  Schmidt's  process  was  tried  on  the  large  scale  in  an  Austrian 
candle  works.  The  quantity  of  liquid  unsaponifiable  substance  ob- 
tained was,  however,  so  large  that  commercial  success  was  out  of  the 
question." 

Many  processes  based  on  the  well-known  action  of  sulfuric  acid  on 
oleic  acid  have  been  proposed.  Hydroxy-stearic  acid  is  obtained  by 
steaming  the  product.  It  would  lead  us  too  far  from  the  present 
subject  to  enter  into  any  further  discussion  of  these  reactions. 


PROCESSES  INVOLVING  APPLICATION  OF  ELECTRICITY  ' 

In  1886  Weineck  §  called  attention  to  the  possibility  of  electrolytic 
addition  of  hydrogen  to  oleic  acid.  Kuess  ||  later  attempted  to  apply 
the  electric  current  in  the  steam  distillation  of  fatty  acids. 

In  patents  taken  out  by  Magnier,  Bragnier  and  Tissier,  If  the  fatty 
material  is  acidified  with  sulfuric  acid,  whereupon  the  acidified  mass 
is  mixed  with  5  to  6  times  its  weight  of  water  and  then  under  a  pressure 
of  5  atmospheres  is  subjected  to  the  action  of  an  electric  current,  which 
generates  hydrogen  in  a  nascent  state. 

An  interesting  method  of  converting  oleic  into  stearic  acid  is  that 
comprised  in  the  Hemptinne  electric  discharge  process.  The  method 

*  Chem.  Ztg.,  1900,  566. 
t  J.  S.  C.  I.,  98  (1883),  200  (1884). 
t  Lewkowitsch,  "Oils,  Fats  and  Waxes,"  p.  664. 
§  Osterr.  Privil.,  10,  400  (July  19,  1886). 
II  Chem.  Ztg.,  1896,  618. 

H  British  Patent  3363,  1900;  German  Patent  126,446,  October  3,  1899,  and 
additional  German  Patent  132,223. 


4  THE  HYDROGENATION  OF  OILS 

is  carried  out  by  interposing  a  thin  layer  of  the  oil  in  the  path  of  an 
electric  discharge,  while  bringing  hydrogen  into  contact  with  the  oil.* 
Fig.  1  shows  the  arrangement  of  apparatus  for  this  purpose.  The 
conversion  is  effected  in  a  chamber  having  an  inlet  pipe  H,  furnishing 
hydrogen  under  constant  pressure.  Oleic  acid  is  supplied  by  a  pipe 
0  to  a  sprinkling  device  which  discharges  the  acid  onto  a  system  of 
parallel  plates  consisting  of  the  glass  plates  G  and  alternately  the  metal 
plates  M,  N.  The  metal  plates  M  are  connected  to  one  pole,  the 
others,  N,  being  connected  with  the  other  pole  of  a  source  of  electricity. 


I_  j— n~f 
,  a  1 1"  ' 

liHy  JLjr  u 


FIG.  1. 


As  the  oil  passes  over  the  plates  the  electrical  discharge  causes  con- 
version of  some  oleic  acid  into  stearic  acid,  and  analogous  compounds 
having  melting  points  in  the  neighborhood  of  69°  C. 

Hemptinne  prefers  to  work  at  pressures  less  than  atmospheric. 
The  yield  is  lower  at  atmospheric  pressure.  By  treatment  in  this 
manner  it  is  not  difficult  to  secure  a  yield  of  20  per  cent  of  stearic  acid. 
Repeated  treatment  permits  even  up  to  about  40  per  cent  yield.  Here, 
as  so  often  elsewhere,  the  effect  of  mass  action  becomes  manifest  and 
as  the  content  of  stearic  acid  increases  the  speed  of  reaction  greatly 
decreases.  Much  better  results  are  obtained  by  saturating  to  the 
extent  of  about  20  per  cent,  removing  the  stearic  acid  by  pressing, 
when  the  oil  of  reduced  stearic  acid  content  is  again  subjected  to  the 
electric  discharge,  and  a  further  20  per  cent  yield  obtained.  The 
oleic  residue  contains  liquid  condensation  products  amounting  to 
about  40  per  cent  of  the  total  weight.  It  is  stated  that  the  presence 
of  these  bodies  does  not  impair  the  market  value  of  what  some  one  has 
termed  "  electrocuted  "  oleic  acid. 


U.  S.  Patent  797,112,  August  15,  1905. 


METHODS  OF  HYDROGENATION  5 

Petersen  *  also  endeavored  to  reduce  oleic  acid  to  stearic  acid  by 
allowing  an  electric  current  to  act  between  nickel  electrodes  on  an 
alcoholic  oleic  acid  solution,  slightly  acidulated  with  sulfuric  acid  or 
preferably  with  hydrochloric  acid.  But  the  yield  of  stearic  acid  was 
small,  even  under  the  most  favorable  conditions,  and  did  not  exceed 
15  to  20  per  cent. 

Petersen  also  endeavored  to  reduce  sodium  oleate  in  aqueous  or 
alcoholic  solution  to  the  stearate.  No  satisfactory  results  were 
obtained. 

C.  F.  Bohringer  and  Sohne  f  obtained  by  the  same  method  much 
better  results  when  using  as  cathodes,  metallic  electrodes,  which  were 
covered  with  a  spongy  layer  of  the  same  metal.  They  recommend  as 
cathodes  platinized  platinum,  and  also  palladium  electrodes  covered 
with  a  spongy  layer  of  palladium-black.  Nickel  electrodes  are  not  as 
effective. 

Bruno  WaserJ  states  that  oleic  acid  or  olein  should  be  sulfonated 
and  freed  from  free  sulfuric  acid  before  adding  hydrogen  electrically 
(cathodic  reduction).  As  an  example,  one  equivalent  of  oleic  acid  is 
mixed  with  two  or  three  equivalents  of  95  per  cent  sulfuric  acid,  the 
temperature  not  being  permitted  to  advance  more  than  5  degrees.  The 
mixture  is  allowed  to  stand  24  hours,  is  then  washed  with  ice  cold 
water  and  dissolved  in  boiling  water.  This  solution  serves  as  catho- 
lyte,  a  30  per  cent  sulfuric  solution  being  the  anode  liquid.  A  di- 
aphragm separates  lead  electrodes.  The  temperature  is  maintained 
at  90°  to  100°  C.  with  a  current  density  of  25  to  100  amperes  per 
square  decimeter,  giving  60  to  70  per  cent  conversion  to  stearic  acid. 

HYDROGENATION  BY  CATALYTIC  ACTION 

Kolbe  §  in  1871  states  that  Saytzeff  reduced  nitrobenzol  to  aniline 
by  passing  the  vapors  of  the  former,  mingled  with  hydrogen,  over 
palladium-black. 

About  twenty-five  years  later  Sabatier  and  Senderens  began  their 
classic  study  of  nickel  and  other  metallic  catalyzers. 

The  work  of  Sabatier  and  Senderens  ||  laid  the  foundation  for  the 

*  Z.  Elektrochemie,  1905,  549. 

t  German  Patents  187,788,  189,332,  1906. 

t  German  Patent  247,454,  March  24,  1911,  and  Seifen.  Ztg.,  1912,  661. 

§  J.  prakt.  Chem.  [2],  4,  418  (1871). 

II  Sabatier  and  Senderens  published  the  results  of  their  earlier  work  in  Comp. 
rend.,  132,  210,  566  and  1254.  A  very  complete  description  of  their  investigations 
appears  in  Ann.  de  Chim.  et  de  Phys.,  1905  (8),  4,  319-488.  See  also  Mailhe  Chem. 
Ztg.,  1907  (31),  1083,  1096,  1117,  1146  and  1158;  Chem.  Ztg.,  1908  (32),  229  and 


6 


THE  HYDROGENATION  OF  OILS 


present  processes  of  hydrogenation  of  oils.  These  distinguished 
chemists  first  recognized  the  effectiveness  of  nickel  and  certain  other 
metals  as  carriers  of  hydrogen  and  they  elaborated  a  series  of  brilliant 
experiments  extending  over  a  number  of  years,  which  demonstrated 
that  unsaturated  compounds,  that  is,  bodies  lacking  in  hydrogen,  could 
be  saturated  or  given  the  full  quota  of  hydrogen  by  contact  with  this 
gas  in  the  presence  of  a  catalyzer  or  carrier,  such  as  finely-divided 
nickel.  By  their  painstaking  labors  the  reaction  was  shown  to  be  one 
of  general  application. 

Fig.  2  shows  the  apparatus  used  by  these  investigators  in  the  hydro- 
genation of  bodies  capable  of  vaporization.     In  this  apparatus,  1  is 


FIG.  2. 


a  hydrogen  generator;  2  and  3  are  wash  bottles;  4  is  a  vaporizer 
containing  the  substance  to  be  converted  into  a  vapor;  5  is  a  hydro- 
gen chamber  containing  nickel  catalyzer  and  heated  by  an  oil  bath; 
and  6  is  a  condenser. 

While  a  good  deal  of  work  has  been  done  on  the  hydrogenation  of 
fatty  oils,  the  literature  on  the  subject  is  not  very  profuse  and  only 
through  the  patents  which  have  been  issued  can  we  gather  from  any 

244;  Willstatter  and  Mayer,  Ber.,  1908  (41),  2199;  Paal  and  Amberger,  Her.,  1905 
(38),  1406  and  2414:  Paal  and  Gerum,  Ber.,  1907  (40),  2209;  1908  (41),  813  and 
2273;  1909  (42),  1553;  Paal  and  Hartmann,  Ber.,  1909  (42),  2239;  Paal  and  Roth, 
Ber.,  1908  (41),  2282;  1909  (42),  1541;  Ipatiew,  Ber.,  1902  (35),  1047;  1904  (37), 
2961;  Chem.  Centralbl.,  1906,  II,  86;  Ber.,  1907  (40),  1270  and  1286;  1908  (41), 
991;  1909  (42),  2089,  2092  and  2100;  Ipatiew,  Jakowlew  and  Rakitin,  Ber.,  1908 
(41),  996;  Ipatiew  and  Philipow,  Ber.,  1908  (41),  1001;  Padoa  and  Carughi,  Chem. 
Centralbl.,  1906,  II,  1011. 


METHODS  OF  HYDROGENATION  7 

published  records  much  that  is  enlightening  as  to  some  of  the  techni- 
cal developments  in  this  industry.  The  patents  concerned  with  the 
matter  have,  moreover,  been  subjected  to  a  great  deal  of  scrutiny 
because  of  the  alleged  basic  character  of  certain  of  them.  For  these 
reasons  the  remainder  of  this  chapter  pertains  very  largely  to 
processes  which  have  been  covered  by  patents  *  in  this  country  or 
abroad. f 

A  German  Patent  139,457,  of  July  26,  1901,  to  J.  B.  Senderens,  is 
probably  the  first  patent  record  having  to  do  with  the  reduction  of 
organic  bodies  by  hydrogen  in  the  presence  of  nickel  catalyzers.  This 
patent  is  for  the  production  of  aniline  from  nitrobenzol  and  involves 
passing  the  latter  body  in  the  form  of  a  vapor  over  heated  nickel, 
copper,  cobalt,  iron  or  palladium  in  the  presence  of  hydrogen.  The 
hydrogen  may  be  in  the  pure  state  or  in  the  form  of  water-gas. 

The  first  disclosure  of  the  possibility  of  hydrogenation  of  oils  in  a 
liquid  state  apparently  comes  from  Leprince  and  Siveke. J  In  Eng- 
land a  corresponding  patent  1515,  of  1903,  was  issued  to  Normann  § 
and  the  latter  patent  has  become  widely  known  because  of  its  alleged 
fundamental  character.  || 


*  Sachs  (Zeitsch.  f ."  angew.  Chem.,  1913,  No.  94,  784)  reports  183  patents  on  oil 
hardening  of  which  there  are  33  German;  22  French;  51  English;  33  United  States; 
9  Belgium;  and  35  in  other  countries. 

f  The  illustrations  immediately  following  are  largely  derived  from  the  drawings  of 
patent  records  or  have  been  prepared  from  written  descriptions.  In  some  cases  all 
details  deemed  unnecessary  in  the  portrayal  of  the  essential  features  of  these  proc- 
esses have  been  omitted.  The  original  records  should,  of  course,  be  consulted  for 
details.  —  Author. 

J  German  Patent  141,029,  August  14,  1902,  Herforder  Maschinenfett  und 
Oelfabrik. 

§  This  English  patent  is  owned  by  a  large  soap  manufacturing  house  in  England 
and  has  been  passed  on  unfavorably  by  the  courts.  See  Appendix. 

II  The  Seifensieder  Zeitung  (1913),  1272,  states  that  German  Patent  141,029 
(Leprince  and  Siveke)  is  controlling  in  that  country  so  far  as  the  use  of  metallic 
catalyzers  for  oil  hardening  is  concerned,  because  this  patent  makes  the  first  dis- 
closure of  the  hydrogenation  of  bodies  in  the  liquid  state  by  simple  addition  of  a 
catalyzer  and  introduction  of  hydrogen.  According  to  the  same  journal  (1913), 
1195,  the  Bremen-Besigheimer  Olfabriken  in  Bremen  has  a  large  plant  for  the  hydro- 
genation of  fats  and  oils  which  at  one  time  was  not  in  use  because  of  patent  disputes 
between  this  concern  and  the  Germania  Company.  The  Bremen  Company  has 
made  arrangements  with  the  patent  owners  and  is  now  operating  the  Bremen  plant. 
(Seifen.  Ztg.  (1913),  1273.) 

Leprince  and  Siveke  (German  Patent  141,029  was  assigned  on  July  22,  1910, 
to  Joseph  Crosfield  &  Sons,  Ltd.,  of  England  and  was  again  assigned  on  August  9, 
1911,  to  Naamlooze  Venootschaap  Anton  Jurgen's  Fabriken,  Oss  in  Holland.  The 
latter  concern  on  the  10th  of  July,  1911  founded  the  Oelwerke  Germania,  G.  M.  b.  H., 


8  THE  HYDROGENATION  OF  OILS 

at  Emmerich,  on  the  Rhine.  The  plant  is  reported  to  have  been  put  into  operation 
in  the  Spring  of  1912  —  almost  ten  years  after  the  application  for  German  patent 
141,029. 

The  contentions  of  Professor  Erdmann  (Seifen.  Ztg.  (1914),  32)  present  cer- 
tain points  of  interest.  Referring  to  German  Patent  141,029  which  was  applied 
for  in  1902  and  granted  in  1903,  Erdmann  states  that  eight  years  later  —  without 
being  used  regularly  on  a  large  scale  in  Germany  —  the  rights  were  sold  in  England 
to  Crosfield  &  Sons.  The  requirements  for  the  successful  hardening  of  oils  by  the 
use  of  metallic  nickel  as  a  catalyst  are  regarded  as  having  been  here  given  for  the 
first  time. 

The  German  patent  application  B.  62,366,  IV,  12°,  of  Bedford,  Erdmann  and 
Williams  for  hydrogenating  oils  with  the  aid  of  metallic  oxides,  was  entered  on  March 
16,  1911,  together  with  the  English  priority  of  Dec.  20,  1910,  a  time  therefore  when 
the  Germania  Werke  did  not  exist.  In  addition,  it  is  stated,  Bedford  and  his  col- 
leagues immediately  started  in  to  actually  materialize  their  original  discoveries  and 
ideas  on  a  large  scale;  their  experimental  plant  had  been  working  for  a  considerable 
period  and  in  Germany  at  that  time  oils  had  not  been  hardened  on  a  manufacturing 
scale. 

It  is  not  true,  Erdmann  states,  that  the  process  of  German  patent  141,029  was 
the  first  solution  of  the  problem  of  the  direct  addition  of  hydrogen  to  unsaturated 
fatty  bodies.  It  does  not  cover  the  direct  addition  of  hydrogen  —  a  process  for 
the  direct  addition  of  free  hydrogen  by  means  of  a  catalyst  involves  a  contradiction 
of  terms  —  but  aims  at  the  indirect  addition  to  an  unsaturated  fatty  substance 
by  means  of  a  catalytic  hydrogen  carrier  in  just  the  same  way  as  this  had  already 
been  accomplished  previously  by  Karl  Peters  (Monatshefte  f.  Chemie,  1886  [7],  552), 
and  Reformatoky  (J.  prakt.  Chemie  N.  S.,  1890  [41],  437)  in  the  hydrogenation  of 
oleic  acid  to  stearic  acid  by  the  use  of  iodine  as  the  hydrogen  carrier. 

At  the  time  of  the  application  for  German  patent  141,029  —  that  is,  in  1902  — 
Erdmann  pbserves  that  the  transformation  of  unsaturated  compounds  contained  in 
liquids  to  saturated  compounds  by  means  of  the  introduction  of  free  hydrogen  into 
the  liquid  with  the  aid  of  a  catalyst  was  not  entirely  unknown.  For  example,  in  1873, 
Saytzeff  (in  Kolbe's  laboratory)  obtained  aminophenol  and  methylamin  by  the  in- 
troduction of  free  hydrogen  into  a  solution  of  nitrophenol  or  nitromethane  in  the 
presence  of  finely-divided  palladium.  (See  J.  prakt.  Chemie.  N.  S.  [6],  128.)  In 
practically  the  same  way,  oleic  acid  could  be  changed  to  stearic  acid  as  Fokin  later 
showed  (Chem.  Centralbl.  (1907),  II,  1324).  Hence  Erdmann  claims  it  is  not  true 
that  the  existence  of  the  discovery  represented  by  German  patent  141,029  can  be 
looked  upon  as  the  first  time  that  a  means  was  found  to  saturate  unsaturated  sub- 
stances in  the  liquid  state  by  means  of  free  hydrogen. 

In  case  any  discovery  can  be  found  set  forth  in  Patent  141,029  —  which  according 
to  the  statements  of  the  English  courts  is  at  least  very  questionable  —  the  new 
idea,  Erdmann  contends,  can  only  be  that  the  two  steps: 

(a)  Hydrogenation  of  liquid  organic  substances  by  the  introduction  of  free  hydro- 
gen in  the  presence  of  a  finely-divided  metallic  catalyst,  and 

(6)  Hydrogenation  of  unsaturated  fatty  substances  in  the  presence  of  a  non- 
metallic  or  not  finely-divided  metallic  catalyst, 

which  steps  were  known  separately,  are  combined  with  one  another  in  this  way, 
that  fatty  substances  are  hydrogenated  by  the  introduction  of  free  hydrogen  in  the 
presence  of  a  finely-divided,  metallic  catalyst,  particularly  nickel  which  was  already 
known  to  be  a  hydrogen  carrier.  Metals,  also,  —  for  example  zinc  —  had  been  pro- 


/ 


METHODS  OF  HYDROGENATION 


9 


Normann  states  that  he  may  carry  out  the  hydrogenation  of  oils  by 
treatment  either  in  the  form  of  vapors  or  as  liquids.  In  the  former 
case  the  fatty  acid  vapors  together  with  hydrogen  may  be  caused  to 
pass  over  catalytic  material  carried  by  a  pumice  stone  support.  This 
may  be  represented  by  Fig.  3  in  which  A  is  a  bed  containing  granular 
pumice  coated  with  a  metal  catalyzer.  0  is  an  inlet  for  oil  vapors  and 
H  is  an  inlet  for  hydrogen.  The  mixture  passes  through  the  tube  A 
and  the  converted  material  is  withdrawn  at  B.  Normann  notes, 
however,  that  it  is  sufficient  to  expose  the  fat  or  fatty  acid  in  a  liquid 


0 


FIG.  3. 


condition  to  the  action  of  hydrogen  and  the  catalytic  substance.  He 
states  that,  for  instance,  if  fine  nickel  powder  obtained  by  the  reduc- 
tion of  nickel  oxide  in  a  current  of  hydrogen  is  added  to  oleic  acid, 
the  latter  heated  over  an  oil  bath  and  a  strong  current  of  hydrogen 
caused  to  pass  through  it  for  a  considerable  time,  the  oleic  acid  may 
be  completely  converted  into  stearic  acid. 

Fig.  4  shows  very  simple  apparatus,  such  as  might  have  been  used 
by  Normann  to  this  end.  A  is  a  vessel  containing  oil  0  in  which  fine 
particles  of  nickel  are  suspended  while  a  strong  current  of  hydrogen 
from  the  pipe  H  affords  the  hydrogen  requisite  for  reduction  of  the  oil. 
By  this  means  Normann  treated  the  fatty  acid  of  tallow,  having  an 

posed  for  the  hydrogenation  of  oleic  acid  before  1903  (compare  Tissier,  Chem.  Ztg., 
1899  [23],  822). 

Normann  (Seifen.  Ztg.  (1913),  1381)  regards  the  employment  of  metal  oxides 
or  organic  salts  as  catalyzers  to  fall  within  the  scope  of  the  Leprince  and  Siveke 
(Normann)  German  patent  141,029,  because  of  the  reduction  occurring  when  these 
metallic  compounds  are  exposed  to  hydrogen  in  the  hardening  process.  Meigen  and 
Bartels  (J.  prakt.  Chem.  1914,  290)  support  Normann's  contention.  The  assertions 
of  Erdmann  regarding  the  existence  of  nickel  suboxide  when  hardening  oils  with 
nickel  oxide  catalyzers  are  challenged  by  the  Olwerke  Germania  (Seifen.  Ztg.  1914, 
209)  and  it  is  claimed  that  metallic  nickel  forms  under  the  conditions  to  which  Iho 
oxide  is  subjected.  In  this  connection,  a  brief  review  of  Ipatieff's  work  is  given. 


10 


THE  HYDROGENATION  OF  OILS 


iodine  number  of  35  and  melting  at  about  46,  thereby  converting  it 
into  a  body  of  improved  color  having  an  iodine  number  of  about  10 
and  a  melting  point  of  about  58.  Normann  also  states  that  commer- 
cial gas  mixtures,  such  as  water-gas,  may 
be  used  in  lieu  of  pure  hydrogen. 

The  disclosures  of  the  Normann  patent 
are,  however,  rather  meagre  and  can  hardly 
be  considered  to  comprehensively  traverse 
the  difficulties  encountered  in  the  practical 
hydrogenation  of  oils  in  a  liquid  state. 

Day  has  brought  out  a  process  *  in  which 
he  treats,  not  fatty  oils,  but  hydrocarbon 
oils,  with  hydrogen  in  the  presence  of  what 
he  terms  a  porous  absorptive  substance 
mentioning  palladium  black,  platinum 
sponge,  zinc  dust,  fuller's  earth  and  other 
clays.  Fig.  5  shows  one  method  proposed  by  Day  to  this  end. 

The  upper  chamber  A  is  filled  with  hydrocarbon  oil,  and  porous  ab- 
sorptive material,  such  as  palladium  black,  is  introduced  into  the  inter- 


1 


F 


A 


Jf 


FIG.  5. 


FIG.  6. 


mediate  chamber  C  by  way  of  the  plugged  orifice  D.  Any  air  present 
in  C  may  be  expelled  by  flushing  out  with  hydrogen  or  an  indifferent 
gas.  Hydrogen  is  then  admitted  by  the  pipe  H  until  the  porous 


*  If.  S.  Patent  826,089,  July  17,  1906. 


METHODS  OF  HYDROGENATION  11 

material  has  absorbed  its  full  quota.  The  hydrogen  gas  may  be 
admitted  under  a  pressure  of  100  pounds  or  more  to  the  square  inch. 
When  the  porous  material  in  C  has  become  properly  charged  with 
hydrogen,  the  oil  is  allowed  to  run  from  the  chamber  A  through  the 
chamber  C  into  the  collecting  chamber  E,  hydrogen  being  introduced 
as  required  by  the  pipe  H. 

In  the  place  of  hydrogen,  Day  states  that  ethylene  or  other  hydrogen- 
carrying  gas  or  vapor  may  be  employed.  By  this  treatment  the  dis- 
agreeable odor  of  hydrocarbon  oil  is  in  great  part  removed  and  the 
burning  qualities  of  the  oil  improved.  When  palladium  black  is  used 
it  is  recommended  that  a  proportion  of  one-half  ounce  to  the  gallon  of 
oil  be  taken. 

Fig.  6  shows  a  modification  of  Day's  process.  A  is  an  oil  still,  in  the 
lower  part  of  which  the  perforated  pipe  H  serves  for  the  admission 
of  hydrogen.  Palladium  black  or  other  porous  absorptive  material 
forms  a  layer  C,  on  a  screen  above  the  hydrogen  inlet.  0  shows  the 
charge  of  oil.  In  operating  this  apparatus  the  layer  of  material  C  is 
first  charged  with  hydrogen  and  then  oil  run  into  the  still.  Distilla- 
tion is  carried  out  while  hydrogen  gas  is  being  forced  through  the 
absorptive  material  and  oil.* 

*  The  removal  of  sulfur  from  petroleum  is  effected  according  to  Schiller  (U.  S. 
Patent  580,652,  April  13,  1897),  by  generating  hydrogen  in  a  nascent  condition  in  the 
oil  during  the  distillation  of  the  latter.  It  is  claimed  that  sulfur  is  thus  eliminated 
as  hydrogen  sulfide.  Zinc  dust  and  an  alkaline  hydrate,  such  as  dry  powdered 
caustic  soda,  are  employed  to  generate  hydrogen.  These  are  added  to  the  oil  under- 
going distillation.  Huston  (U.  S.  Patent  486,406,  Nov.  15,  1892)  proposes  to  re- 
move sulfur  by  heating  the  vapors  of  a  sulfur-containing  petroleum  oil  admixed  with 
steam  to  a  temperature  of  900°  F.  at  which  temperature  it  is  said  that  the  hydro- 
gen of  the  water  vapor  unites  with  the  sulfur,  forming  hydrogen  sulfide.  Hawes 
(U.  S.  Patent  444,833,  Jan.  20,  1891)  avails  of  the  same  reaction  and  brings  a  mixture 
of  vapor  of  hydrocarbon  and  water  into  contact  with  gravel  contained  in  a  chamber 
which  is  heated  to  a  temperature  of  400°  to  600°  F.  Dubbs  (U.  S.  Patent  470,911, 
March  15,  1892)  forces  a  gas  rich  in  hydrogen  through  oil  in  a  still  to  remove  sulfur 
as  hydrogen  sulfide.  Stevens  (U.  S.  Patent  414,601,  Nov.  5,  1889)  claims  steam 
reacts  with  the  sulfur  present  in  petroleum  oils  to  form  sulfurous  acid,  while  the 
hydrogen  thus  liberated  combines  with  the  carbon  of  the  oil,  resulting  in  an  in- 
creased yield  of  light  oil.  See  also  Turner  (U.  S.  Patent  1,046,683,  Dec.  10,  1912)  and 
Noad  (U.  S.  Patent  971,468,  Sept.  27,  1910).  Hall  (U.  S.  Patent  362,672,  Nov.  8, 
1887)  uses  "converting  surfaces"  of  granite.  Wilkinson  (U.  S.  Patent  145,707, 
Dec.  16,  1873)  has  specified  the  distillation  of  petroleum  oils  with  hydrogen. 

The  French  patents  to  Sabatier,  400,141,  and  to  Haller,  Sabatier  and  Senderens, 
376,496,  are  of  interest  in  this  connection. 

In  studying  the  effects  of  catalytic  agents  upon  the  decomposition  of  petroleum 
oils,  100  grams  of  coarsely  powdered  porous  earthenware  upon  which  nickel  had  been 
reduced  in  metallic  form  were  impregnated  with  10  to  12  grams  of  the  oil,  and  heated 


12 


THE  HYDROGENATION  OF  OILS 


The  British  Patent  to  Bedford  and  Williams,  2520,  of  1907,  contains 
probably  the  first  published  description  of  a  method  of  exposing  oil  to 
the  action  of  hydrogen  by  forming  the  oil  in  a  spray  or  films  in  an 
atmosphere  of  hydrogen  and  in  contact  with  a  catalyzer  of  the  nickel 
type.  In  this  manner  the  patentees  state  they  converted  linseed  oil 
into  a  hard  fat  solidifying  at  53°  C.  Oleic  acid  was  converted  into 
stearic  acid  having  a  melting  point  of  69°  C.,  and  paraffin  wax  they 
state  had  its  solidifying  point  raised  3°  C.  by  the  treatment. 

A  peculiar  manner  of  treatment  has  been  shown  by  Schwoerer,* 
which  will  be  made  clear  by  Fig.  7.  The  receptacle  A,  which  is  heated 


FIG.  7. 


FIG.  8. 


by  the  steam  jacket  S,  is  provided  with  what  Schwoerer  calls  a  helical 
pan,  shown  at  B.  The  underside  of  the  pan  carries  a  layer  of  nickelized 
asbestos.  0  is  an  inlet  for  oil  and  hydrogen,  and  D  an  outlet  for  the 
treated  material. 

Schwoerer  states  that  he  first  mixes  fatty  acid  and  hydrogen  by 
atomizing  the  oil  with  a  jet  of  superheated  steam  in  the  presence  of 
hydrogen  and  conducts  this  mixture  through  the  pipe  0,  into  the 
chamber  A.  The  temperature  maintained  in  the  apparatus  is  from 

at  regulated  temperatures  from  180°  to  500°  C.  in  a  current  of  hydrogen.  The  gases 
were  collected  and  analyzed,  while  the  distillates  were  compared  with  those  obtained 
under  parallel  conditions,  but  without  the  presence  of  the  catalytic  agent.  No 
lowering  of  the  vapor  pressure  appeared  to  be  caused  by  the  catalytic  action.  Vari- 
ous proportions  (according  to  the  partial  pressure,  temperature,  etc.)  of  hydrogen, 
methane,  ethane  and  heavy  hydrocarbons  were  produced  under  the  influence  of 
the  catalytic  agent,  while  the  distillates  were  of  quite  different  character  from  those 
yielded  by  the  oil  alone.  Ubbelohde  and  Woronin,  J.  S.  C.  I.,  1911,  1242;  Petro- 
leum 1911  [7],  9. 

*  U.  S.  Patent  902,177,  Oct.  27,  1908. 


METHODS  OF  HYDROGENATION  13 

250°  to  270°  C.  Vapors  of  oleic  acid  come  in  contact  with  the  layer  of 
catalyzer  on  the  underside  of  the  helical  pan  and  are  converted  into 
stearic  acid.  The  product  collects,  more  or  less,  in  the  gutter  of  the 
helical  pan  and  is  removed  at  D. 

The  repeated  caution  given  by  Sabatier  to  bring  in  contact  with  the 
catalyzer  only  the  vapors  of  the  material,  doubtless  led  Schwoerer  to 
devise  this  form  of  apparatus. 

Bedford,  presumably  with  the  same  caution  of  Sabatier  in  mind, 
discloses,  in  U.  S.  Patent  949,954,  of  Feb.  22,  1910,  a  process  which 
also  has  to'  do  with  vaporization  of  the  oily  material.  Fig.  8  shows  the 
Bedford  apparatus.  A  still  or  tower  A  carries  two  beds  of  catalyzer 
C  and  C'.  This  is  said  to  be  preferably  nickelized  pumice.  By  means 
of  hydrogen  under  pressure,  oleic  acid  is  sprayed  from  the  pipe  0, 
onto  the  catalyzer  bed  C'.  Hydrogen  is  admitted  through  the  pipe  H. 
A  temperature  of  about  200°  C.  and  a  diminished  pressure  of  about  50 
to  100  mm.  is  maintained  in  the  still  or  tower  A.  The  vapors  of  oleic 
acid  mingled  with  hydrogen  pass  through  the  second  catalyzer  bed  C, 
where  more  or  less  conversion  occurs,  then  pass  to  the  condenser  D,  and 
finally  collect  in  the  receptacle  E.  F  is  a  connection  to  a  vacuum 
pump. 

Neither  this  process  nor  that  of  Schwoerer  is  broadly  applicable 
to  the  treatment  of  glycerides  as  these  cannot  be  vaporized  without 
undue  decomposition.* 

Erdmann  has  taken  out  a  German  Patent  211,669,  of  Jan.  19,  1907, 
involving  passing  an  oil  as  spray  or  mist  into  a  chamber  containing 
nickel  catalyzer  supported  on  pumice  and  the  like.  Fig.  9  probably 
indicates  one  form  suggested  by  Erdmann,  who,  by  the  way,  does  not 
show  any  drawings  in  the  patent.  The  chamber  A  has  a  rotatable 
cylinder  B,  which  is  coated  with  nickel  catalyzer.  In  the  bottom  of 
the  receptacle  is  a  quantity  of  nickelized  pumice.  Oil  enters  at  0  and 
is  atomized  by  hydrogen  entering  at  H .  The  atomized  mixture  im- 
pinges upon  the  rotating  cylinder  B,  then  passes  through  the  bed  C, 
the  oil  being  drawn  off  at  D.  The  excess  of  hydrogen  is  presumably 
vented  in  the  upper  part  of  the  apparatus. 

*  Sabatier  and  Senderens,  Annales  de  Chimie  et  de  Physique  [81,  4,  335  (1905), 
state  that  "Le  me"tal  ne  soit  jamais  mouille"  par  un  afflux  excessif  du  liquide  que 
Ton  traite,  ou  a  la  suite  d'un  abaissement  accidental  de  la  temperature  du  tube." 
They  further  say  that  in  the  preparation  of  cyclohexanol  and  its  homologues  from 
phenol  or  cresol  at  a  temperalure  but  slightly  above  the  boiling  points  of  the  latter 
bodies,  sometimes  by  their  condensation,  the  nickel  becomes  moistened  and  imme- 
diately becomes  almost  inactive,  due,  no  doubt,  to  the  surface  becoming  permanently 
changed  in  character  by  contact  with  the  liquid  phenol  or  cresol. 


THE  HYDROGENATION  OF  OILS 


A  second  modification  (Fig.  10)  involves  a  tower  A,  filled  with 
catalyzer  C,  which  may  be  in  the  form  of  nickel  supported  on  coarse 
fragments  of  pumice.  By  the  pipe  0  oil  is  admitted  to  the  chamber 
in  an  atomized  or  finely-divided  state.  Hydrogen  enters  by  the  pipe 


FIG.  9. 


FIG.  10. 


H.  Erdmann  states  that  the  temperature  of  treatment  should  be 
from  170°  to  180°  C.  .  The  treated  oil  is  drawn  off  at  D  while  the 
excess  of  hydrogen  passes  away  at  B. 

In  a  supplement  patent  221,890,  of  1909,  Erdmann  recommends  the 
steam  distillation  from  the  reaction  chamber  of  the  saturated  product 
under  diminished  pressure. 

Vereinigte  Chemische  Werke  A.  G.*  make  use  of  a  palladium  cata- 
lyzer precipitated  on  an  indifferent  body  as  a  carrier  and  recommend 
as  carriers  finely-divided  metals  which  do  not  have  anti-catalytic 
properties,  also  metal  oxides  and  carbonates.  Under  these  circum- 
stances it  is  stated  that  one  part  of  palladium  is  sufficient  to  convert 
in  a  few  hours  100,000  parts  of  oily  material  to  a  firm  mass.  They 
recommend  the  use  of  a  hydrogen  pressure  of  two  to  three  atmospheres 
and  a  temperature  somewhat  above  the  solidification  point  of  the 
saturated  fat.  They  caution  against  arsenic,  hydrogen  phosphide 

*  German  Patent  236,488,  Aug.  6,  1910;  also  British  Patent  18,642,  1911. 


METHODS  OF  HYDROGENATION 


15 


and  sulfide,  liquid  hydrocarbons  and  carbon  bisulfide,  chloroform, 
acetone  and  free  mineral  acids  as  being  destructive  to  the  activity  of 
the  catalyzer. 

Kayser  *  describes  a  process  of  treating  oil  with  metallic  catalyzer 
consisting  in  mechanically  agitating  the  oil  and  catalyzer  in  the 
presence  of  hydrogen,  preferably  under  pressure.  One  form  of  the 
apparatus  indicated  by  Kayser  for  this  purpose  is  diagrammatically 
represented  by  Fig.  11. 


O 


FIG.  11. 


Here  A  is  a  closed  horizontal  cylindrical  vessel  in  which  is  a  paddle 
wheel  D,  made  up  of  blades  carrying  wire  gauze.  The  paddle  wheel 
is  rotated  by  a  driving  gear  at  B.  In  the  upper  part  of  the  tank  is  an 
inlet  for  charging  oil  and  presumably  also  the  catalyzer,  the  oil  being 
admitted  to  the  tank  in  an  amount  sufficient  to  fill  to  perhaps  one- 
fourth  or  one-fifth  the  entire  capacity.  Hydrogen  is  admitted  at  H 
and  passes,  by  the  three-way  cock  7,  to  the  compression  pump  J,  going 
from  there  to  the  treating  receptacle.  At  the  opposite  end  of  the  tank 
is  an  exhaust  pipe  L,  carrying  a  blow-off  valve  M,  for  the  purpose  of 
venting  the  unabsorbed  hydrogen.  The  temperature  of  treatment 
is  stated  to  be  about  150°  to  160°  C.  Although  the  claims  call  for  the 
use  of  hydrogen  under  pressure,  no  working  pressures  are  specified. 
Fig.  12  shows  diagrammatically  one  form  of  construction  of  the  screen- 
covered  paddle  wheel  used  by  Kayser. 

In  another  U.  S.  Patent  1,008,474,  of  Nov.  14,  1911,  Kayser  sets 

*  U.  S.  Patent  1,004,035,  Sept.  26,  1911. 


16 


THE  HYDROGENATION  OF  OILS 


forth  the  use  of  an  inert  pulverulent  material  such  as  kieselguhr  as  a 
carrier  for  the  nickel  catalyzer,  he  apparently  having  determined,  as 
did  Sabatier  and  others,  that  in  some  cases  hydrogenation  is  more  rapid 


FIG.  12. 


or  complete  when  a  carrier  for  the  catalyzer  is  used;  and  he  claims  the 
process  of  hydrogenating  oil  involving  agitation  of  a  metal-impreg- 
nated inert  pulverulent  carrier  (kieselguhr)  with  a  fatty  oil  in  the 

presence  of  hydrogen.  It  is  commonly 
understood  that  the  Kayser  process  is 
in  operation  on  a  large  scale  in  this 
country.* 

Two  patents  relating  to  the  spraying 
of  oil  into  a  chamber  containing  com- 
pressed hydrogen  have  attracted  some 
attention  abroad.  One  of  these  is 
British  Patent  7726,  of  1910,  to  Testrup, 
and  the  other  is  to  Wilbuschewitch 
which  finds  its  counterpart  here  in 
U.  S.  Patent  1,024,758,  of  April  30, 
1912.  Fig.  13  shows  the  elements  of 
the  Testrup  process. 

Oil  and  catalyzer  are  pumped  through 

the  pipe  0  into  the  tank  A,  and  hydrogen  is  admitted  by  the  pipe  H 
to  furnish  a  gas  pressure  of,  say,  15  atmospheres.  The  tubes  B  are 

*  The  Kayser  patents  are  assigned  to  the  Proctor  and  Gamble  Co.,  which  concern 
is  a  large  producer  of  hardened  oil.  A  product  termed  "Crisco"  is  used  as  a  sub- 
stitute for  lard. 


FIG.  13. 


METHODS  OF  HYDROGEN  AT  ION 


17 


heated  by  steam  and  the  stirrer  C  circulates  the  oil  and  catalyzer  in 
the  tank  A,  until  the  oil  has  become  heated  and  presumably  some- 
what hydrogenated.  The  oil  is  allowed  to  pass  into  the  adjacent 
tank  E,  entering  this  tank  by  the  spray  nozzle  F.  Hydrogen  gas  is 
admitted  to  the  tank  E  from  the  tank  A,  so  as  to  afford  a  pressure 
of,  say,  12  atmospheres  in  the  tank  E.  A  series  of  tanks  may  be 
arranged  with  a  constantly  decreasing  pressure  so  that  the  differential 
pressure  enables  the  spraying  of  the  oil  from  tank  to  tank.  Testrup 
states  that  spraying  the  material  ten  or  fifteen  times  is  sufficient  to 
bring  an  oil  of  an  iodine  number  of  110  down  to  an  iodine  number 
of  50. 


FIG.  14. 


According  to  one  form  employing  the  apparatus  shown  in  Fig.  14,  and  treating 
cottonseed  oil,  the  oil,  mixed  with  a  suitable  contact  substance,  such  as  finely- 
divided  palladium  or  preferably  nickel,  is  placed  in  a  vessel  a  provided  with  a  stir- 
ring device  6  comprising  blades  or  like  elements  fixed  to  a  vertical  and  rotatable  shaft 
c  within  it.  The  amount  of  nickel  may  be  about  2  to  3  per  cent  by  weight.  This 
vessel  is  preferably  jacketed  as  at  d,  and  is  heated  by  the  passage  of  heated  fluid 
through  this  jacket,  say  to  about  160°  C.  From  this  chamber  the  oil  is  pumped  by  a 
pump  e  through  a  conduit /and  enters  a  vessel  g,  which  is  jacketed  and  heated  by  tubes 
h,  being  also  provided  with  a  mixing  device  comprising  a  central  tube  and  propeller 
arrangement  i.  Hydrogen  gas  is  supplied  at  high  pressure  from  a  reservoir  j  through 


18 


THE  HYDROGENATION  OF  OILS 


a  duct  k.  The  vessel  g  has  an  educt  I  for  the  material  under  treatment  at  its  base 
and  an  educt  for  hydrogen  m  provided  with  a  loaded  valve  n.  The  duct  m  opens 
into  a  vessel  o  into  which  the  oil  from  the  vessel  g  is  sprayed  by  a  spray  nozzle  p 
attached  to  the  end  of  the  duct  I  by  the  pressure  of  the  gas  in  the  vessel  g.  The  oil 
and  catalyst  thus  exposed  to  the  action  of  the  gas  fall  into  the  base  of  the  vessel  o 
to  be  forced  by  the  pressure  of  the  gas  therein  through  a  duct  to  a  nozzle  r  in  another 
vessel  s  wherein  the  operation  is  repeated.  Several  such  vessels  are  arranged  in  this 
way  in  cascade,  all  being  jacketed  to  allow  of  maintaining  the  desired  temperature. 
The  last  vessel  I  is  provided  with  any  suitable  educt  u  for  the  gas  and  an  educt  v  for 
the  treated  oil  and  catalyst  which  is  passed  to  a  filter  press  w  in  which  the  oil  is 
separated  from  the  catalyst,  the  former  passing  by  a  duct  x  to  a  reservoir  y  and  the 
catalyst  being  returned  to  the  vessel  a  for  which  purpose  the  chute  z  may  be  utilized. 
Should  the  catalyst  have  become  contaminated  with  nickel  soap  it  may  be  purified  as 
by  washing  with  acid.  A  storage  tank  for  the  material  awaiting  treatment  is  indi- 
cated at  1  with  its  duct  2  leading  to  the  vessel  a.  Gauges  for  noting  the  pressure  3  and 
the  level  gauges  4  are  also  employed.  The  temperature  at  which  the  reaction  is  con- 
ducted is  about  160°  to  170°  C.,  and  the  pressure  of  the  hydrogen  in  g  may  be  about 
15  atmospheres,  in  o  say  12  atmospheres,  the  difference  in  pressure  producing  the 
spray.  The  pressure  may  similarly  fall  by  3  atmospheres  for  each  vessel.  It  may 
be  necessary  to  pass  the  substance  again  through  the  ap- 
paratus or  to  provide  several  systems  of  heaters  and 
spraying  devices  in  series  in  order  to  obtain  the  desired 
result  but  by  this  process  the  desired  number  of  repe- 
titions can  be  carried  out  rapidly.* 

Even  such  a  number  of  treatments  are  stated  to  re- 
quire only  about  30  minutes  or  less  and  the  number  of 
treatments  would  depend  largely  on  the  activity  of  the 
catalyst  employed. 

The  Wilbuschewitch  Patent  itself  details  a 
rather  complicated  system,  and  Fig.  15  shows 
only  what  appears  to  be  the  essential  features 
of  the  treating  apparatus.  Several  tanks  or 
autoclaves  are  connected  as  shown  at  A  and 
A'j  oil  entering  the  top  of  the  tank  A  by  the 
pipe  0,  to  form  a  spray  which  in  descending 

meets  an  upward  current  of  hydrogen  entering  by  the  pipe  H.  The 
oil  is  drawn  off  through  the  pipe  0',  and  sprayed  into  the  tank  A'. 
This  time  it  meets  a  current  of  hydrogen  represented  by  the  excess  of 
hydrogen  coming  from  the  tank  A.  The  treated  oil  is  drawn  off  and 
may  be  centrifuged  to  remove  the  catalyzer.  A  pressure  of  nine 
atmospheres  is  recommended  and  the  pressures  may  be  varied  in  the 
different  tanks. 

*  Swedish  Patent  992,  May  27,  1911  (Techno  Chemical  Laboratories,  Ltd.),  on 
the  hydrogenation  of  organic  substances  involving  a  process  which  essentially  con- 
sists in  mixing  catalyzer  with  the  substance  to  be  treated  and  in  subjecting  the 
mixture  in  an  atomized  or  finely-divided  condition  to  the  action  of  hydrogen,  leads 


FIG  15. 


METHODS  OF  HYDROGENATION 


19 


Of  the  Wilbuschewitch  process  Goldschmidt  *  states  that  the  high 
hydrogen  pressures  employed  enable  the  reaction  to  take  place  quickly 
at  temperatures  between  100°  and  160°  C.,  so  that  the  fat  is  not  likely 
to  be  injured  by  the  temperature  to  which  it  is  subjected.  It  should 
be  stated  that  several  years  previous  to  the  date  of  the  Wilbusche- 
witch patent,  Ipatiew  had  noted  and  carefully  studied  the  action  of 
increased  pressure. 

Bedford  and  Williams  have  brought  out  an  interesting  process 
represented  by  U.  S.  Patent  1,026,339,  of  May  14,  1912.  Fig.  16 
shows  the  apparatus  indicated  by  Bedford  and  Williams  for  carrying 
out  the  process.  Oil  is  placed  in  the  receptacle  A,  which  is  heated  by 


FIG.  16. 


FIG.  17. 


a  steam  coil  S.  Metallic  oxide  catalyzer  is  added,  about  1  per  cent 
being  recommended,  and  hydrogen  and  oxygen  or  air  is  introduced 
by  the  pipe  H.  As  a  catalyzer,  nickel  oxide  f  is  recommended  and 
instead  of  the  customary  hydrogenating  temperatures  of  150°  to 
170°  C.,  a  temperature  of  about  250°  C.  is  employed.  While  hydro- 
gen alone  may  be  used  for  the  purpose,  the  inventors  recommend  and 
claim  treatment  of  the  oil  with  a  mixture  of  hydrogen  and  oxygen  to 
form  hydroxy  fatty  acids  or  their  glycerides. 

A  process  for  the  conversion  of  fatty  acids  or  their  glycerides  into 
saturated  bodies  in  which  a  finely-divided  metal  oxide  serves  as  a 
catalyzer  is  described  by  Bedford,  Williams  and  Erdmann,  J  and  the 
reaction  is  carried  out  under  pressures  ranging  from  atmospheric 
pressure  up  to  but  not  exceeding  20  atmospheres.  Nickel  oxide  is 
especially  recommended  as  the  catalytic  material. 

the  editor  of  Cherr.iker  Zeitung  (Chem.  Zeit.  Rep.  (1913),  320)  to  make  the  comment 
that  it  is  somewhat  questionable  according  to  other  investigations  which  have  been 
made  in  this  direction,  whether  this  process  is  practical  for  the  manufacture  of 
edible  fats  and  the  like. 

*  Chem.  Ztg.,  1912,  945. 

f  Previously  used  by  Ipatiew. 

j  Siefen.  Ztg.,  1913,  1413. 


20  THE  HYDROGENATION  OF  OILS 

Shukoff  *  claims  the  process  of  hydrogenating  oils  by  means  of  nickel 
derived  from  the  decomposition  of  nickel  carbonyl.  The  carbonyl 
may  be  obtained  from  reduced  metallic  nickel  by  passing  carbon 
monoxide  over  it  at  a  low  temperature.  Nickel  carbonyl  is  soluble  in 
oil  and  is  very  readily  taken  up  by  gases.  On  heating  to  a  tempera- 
ture of  200  degrees  or  so,  the  carbonyl  is  decomposed,  setting  free,  in 
a  nascent  state,  metallic  nickel  which  acts  as  a  catalyzer.  Shukoff 
makes  use  of  this  reaction  of  nickel  carbonyl  by  the  method  indicated 
by  Fig.  17.  Carbon  monoxide  is  passed  by  the  pipe  G  into  the  tube 
B,  containing  finely-divided  nickel  and  the  nickel  carbonyl  formed  is 
conducted  to  the  oil  0,  which  is  heated  to  about  180  degrees.  After 
sufficient  nickel  catalyzer  has  formed  in  the  oil,  the  carbon  monoxide 
stream  is  cut  off,  the  temperature  raised  to  220°  or  240°  C.  and  hydro- 
gen gas  introduced  by  the  pipe  H  to  bring  about  hydrogenation. 

Schukoff  states  if  nickel  carbonyl  in  a  gaseous  condition  or  a  nickel- 
carbonyl-containing  gas  mixture  is  conducted  into  the  material  to  be 
reduced,  which  may  be  either  in  a  molten  condition  or  in  solution  in  a 
suitable  solvent,  it  is  found,  when  the  temperature  advances  beyond 
the  temperature  of  dissociation  of  nickel  carbonyl,  that  metallic  nickel 
in  an  extremely  finely-divided  state  is  separated  and  that  the  division 
obtained  in  this  way  is  so  fine  as  to  cause  the  reaction  mixture  to 
appear  black  in  color,  and  the  separated  nickel  settles  only  after  very 
long  standing.  As  an  example :  Into  8  kilos  of  cottonseed  oil  warmed 
to  180°  C.  a  slow  stream  of  400  liters  of  carbon  monoxide  is  passed, 
which  carbon  monoxide  has  previously  passed  over  a  long  layer  of 
metallic  nickel  warmed  to  about  60°  C.;  finely-divided  active  nickel 
separates  in  the  oil;  the  stream  of  carbon  monoxide  is  then  inter- 
rupted, the  temperature  raised  to  230°  to  240°  C.,  and  hydrogen  as 
a  slow  stream  is  run  into  the  mixture  during  a  period  of  five  to  six 
hours  in  an  amount  of  3000  liters.  The  reaction  mixture  on  cooling 
is  completely  hard;  by  filtration  the  nickel  can  be  removed  and  the 
product  eventually  converted  into  stearic  acid. 

Day  has  taken  out  U.  S.  Patent  1,004,632,  of  Oct.  3,  1911,  supple- 
menting his  earlier  patent  on  the  treatment  of  hydrocarbon  oils  with 
hydrogen.  In  the  present  instance  tubes  packed  with  catalyzer  are 
placed  in  an  oil  still  in  such  a  manner  that  vapors  from  the  oil  may  pass 
through  the  catalyzer  tube  in  conjunction  with  hydrogen  while  being 
superheated  by  exterior  contact  of  the  tubes  with  boiling  oil. 

An  English  Patent,  23,997,  of  1909,  to  Phillips  and  Bulteel  claims 

*  German  Patent  241,823,  Jan.  18,  1910.  See  also  H.  Kamps,  Belgian  Patent 
246,975;  Seifen.  Ztg.,  1912,  1339.  U.  S.  Patents,  738,303,  777,848  and  943,627  are 
of  incidental  interest. 


METHODS  OF  HYDROGENATION 


21 


to  convert  mineral  oils  into  oils  of  lower  specific  gravity  by  heating 
with  hydrogen  in  the  presence  of  nickel  or  other  catalytic  agents. 
They  state  that  the  mixture  of  oil,  gas  and  catalyst  may  be  blown  into 
a  heated  cylinder  and  the  jet  given  a  gyratory  motion  either  by  means 
of  a  nozzle  revolving  about  its  axis  or  by  injecting  the  mixture  tan- 
gentially  to  the  periphery.  In  the  latter  case  they  state  that  the 
cylinder  may  have  an  axial  core.* 

The  firm  of  H.  Schlinck  &  Co.,  of  Hamburg,  Germany,  f  hydrogenate 
oil  by  passage  through  a  centrifuge,  the  drum  of  which  carries  a  porous 
lining  supporting  palladium  catalyzer  which  offers  a  frictional  resist- 
ance to  the  passage  of  the  oil.  Fig.  18  shows  a  centrifugal  drum  a, 
which  is  closed  at  the  top  and  can  be  heated.  Oil  and  hydrogen  are 
introduced  through  the  pipe  6.  Openings  are  provided  in  the  walls 
of  the  drum  in  which  is  placed  rough  or  porous  material  covered  with 
precipitated  palladium.  Several  drums  may  be  arranged  in  series 


R 


FIG.  18. 


FIG.  19. 


*  In  the  treatment  of  hydrocarbons  with  superheated  steam  Hausmann  and 
Pilat  (German  Patent  227,178,  1909)  recommend  as  catalyzers  the  oxides  of  iron, 
lead,  cerium  and  manganese,  also  iron  sulfate  and  calcium  manganite.  Richter 
(German  Patent  240,760,  1910)  makes  use  of  active  carbon  as  a  carrier  for  oxygen 
in  the  treatment  of  petroleum  and  other  oils.  Leffer  (British  Patent  2328,  1912) 
distils  petroleum  oil  under  pressure  while  circulating  an  inert  gas  through  the  body 
of  oil  in  the  still.  Leffer  mentions  hydrogen  among  the  inert  gases  suitable  for 
the  purpose.  Lamplough  (British  Patent  19,702,  1912)  proposes  to  effect  reaction 
between  petroleum  oil  and  water  by  passing  a  mixture  of  the  vapors  of  these  bodies 
over  rods  of  metallic  nickel  while  subjecting  the  vapors  to  a  pressure  and  to  a  tem- 
perature approaching  a  dull  red  heat.  From  20  to  60  parts  of  water  are  used  to  IOC 
parts  of  oil.  Dibdin  and  Woltereck  (British  Patent  19,152,  1901)  bring  a  mixture 
of  superheated  steam  and  petroleum  oil  into  contact  with  iron,  copper  and  other 
metals  maintained  at  a  bright  orange  heat  to  effect  the  simultaneous  decomposition 
of  the  steam  and  hydrocarbon.  They  also  mention  (British  Patent  26,666,  1905) 
the  use  of  " protoperoxide "  of  iron. 

t  British  Patent  8147,  1911.  The  corresponding  patent  in  the  United  States  is 
1,082,707,  Dec.  30,  1913. 


22 


THE  HYDROGENATION  OF  OILS 


through  which  the  oil  may  be  caused  to  progress  until  sufficiently 
hydrogcnated. 

Ellis  *  uses  a  stationary  catalyzer,  filling  tubes  with  the  material  in 
granular  form  and  allowing  oil  to  flow  through  the  tubes  while  passing 
hydrogen  in  an  opposite  direction.  Fig.  19  shows  a  three-section 
apparatus  with  the  catalyzer  tubes  T,  Tl  and  T'2,  heated  by  the  jackets 
SS.  Oil  from  tank  0  flows  through  the  apparatus  while  hydrogen, 
admitted  by  the  pipe  H,  passes  through  in  an  opposite  direction. 
The  arrangement  permits  of  differential  heating  so  that,  for  example, 
the  oil  may  be  heated  to  a  temperature  corresponding  to  its  particular 
degree  of  hydrogenation  at  any  given  point,  enabling  a  hydrogenated 
product  free  from  "  burnt  "  odor  to  be  obtained.  Fig.  20  shows  a  ver- 
tical form  of  apparatus,  the  catalyzer  being  shown  at  C  in  the  tube  A. 


FIG.  21. 


Oil  is  introduced  by  the  pipe  0,  and  passes  into  the  tube  or  cylinder  A. 
The  pump  P  causes  oil  to  circulate  from  the  top  to  the  bottom  of 
the  apparatus  through  the  pipe  B.  Hydrogen  gas  admitted  at  H  is 
pumped  into  the  bottom  of  the  cylinder  A,  and  the  excess  is  withdrawn 
at  the  top  by  the  pipe  D,  passing  through  the  drier  E,  and  back  into 
the  treating  cylinder.  Oil  may  be  continuously  fed  through  the  pipe 
0  in  the  upper  part  and  the  treated  product  withdrawn  at  the  same 
rate  at  the  lower  part  of  the  apparatus. 

In  another  form  f  of  the  apparatus,  the  catalyzer  is  placed  in  trays 
or  baskets  as  shown  by  Fig.  21  at  C.  The  oil  travels  in  a  cyclic  path 
downward  through  several  layers  of  catalyzer,  and  hydrogen  gas  passes 
in  an  opposite  direction.  Separation  of  the  catalyzer  in  layers  in  this 
manner  enables  the  hydrogen  to  pass  more  uniformly  through  the 

*  U.  S.  Patent  1,026,156,  May  14,  1912.  See  also  U.  S.  Patent  1,052,469,  Feb. 
11,  1913. 

t  U.  S.  Patent  1,040,531,  Oct.  8,  1912. 


METHODS  OF  HYDROGENATION 


23 


catalyzer  bed.  If  the  catalyzer  forms  a  bed  of  considerable  depth  and 
width,  the  gas  in  taking  the  path  of  least  resistance  is  liable  not  to 
come  in  contact  with  some  parts  of  the  bed. 

The  activity  of  a  properly  made  catalyzer  is  oftentimes  surprising. 
In  the  case  of  a  stationary  catalyzer  the  author  has  noted  instances  of 
hydrogenation  where  oil  is  converted  into  a  hardened  fat  by  scarcely 
more  than  momentary  contact  with  the  catalyzer. 

Fig.  22  shows  a  photograph  of  a  small  laboratory  apparatus  for  test- 
ing catalyzers,  consisting  of  an  inclined  tube  containing  the  catalyzer 
and  carried  in  a  heating  jacket.  Oil  is  admitted  at  the  right  and 
hydrogen  at  the  left-hand  end.  Fig.  23  shows  the  catalyzer  tube  at 
the  right  from  which  extends  a  horizontal  tube  supplying  hydrogen 
to  the  catalyzer  tube. 


FIG.  22. 


When  using  a  new  type  of  catalyzer  the  author  started  to  pass  oil 
through  the  catalyzer  tube  and  found  hydrogen  to  be  absorbed  so 
vigorously  by  the  oil  that  instead  of  passing  off  through  an  oil  seal  at 
the  lower  end  of  the  inclined  catalyzer  tube,  the  oil,  curiously  enough, 
was  impelled  against  the  strong  current  of  hydrogen  passing  through 
the  horizontal  tube,  rushing  through  it  to  the  point  indicated  by  the 
hand  of  the  operator  (Fig.  23)  and  there  solidifying,  actually  being 
well  hydrogenated  from  its  brief  passage  through  the  apparatus.  A 


24 


THE  HYDROGENATION  OF  OILS 


peculiar  feature  was  the  advance  of  the  oil  from  the  tube  containing 
catalyzer  far  into  the  tube  through  which  only  the  hydrogen  was 
entering  the  apparatus.  The  travel  of  the  oil  along  the  hydrogen- 
supplying  pipe  in  opposition  to  a  rapid  current  of  hydrogen  indicates 
the  possibility  of  hydrogenating  in  a  very  short  time,  provided  a  cata- 
lyzer of  a  high  degree  of  activity  is  secured. 


FIG.  23. 


On  the  other  hand,  some  catalyzers  of  the  nickel  and  cobalt  type 
when  first  brought  into  contact  with  oil  and  hydrogen  show  for  a  time 
a  certain  degree  of  sluggishness,  but  after  a  period,  their  activity 
rather  suddenly  augments  and  thenceforth  remains  apparent  for  a 
long  period.  This  sluggishness  should  not  be  confounded  with  the 
seeming  initial  inactivity  in  the  hydrogenation  of  oils  containing  con- 
siderable linolein  or  other  highly  unsaturated  bodies.  In  such  cases 
the  rate  of  "  hardening  "  (increase  in  melting  point)  is  slow  at  first 
and  later  progresses  more  rapidly.  Hydrogenation,  in  some  cases  at 
least,  apparently  proceeds  selectively  with  initial  formation  of  olein 
from  linolein.  Later  the  olein  is  transformed  into  stearin  with  the 
observed  more  rapid  increase  of  titer.* 

*  Mailhe  (Rev.  gen.  des  Sciences,  1913,  653)  makes  note  that  he  has  seen  cotton- 
seed oil  hardened  to  a  high  titer  by  twenty  minutes  exposure  to  hydrogen  and  cata-  , 
lytic  material. 


METHODS  OF  HYDROGENATION 


25 


Marcusson  and  Meyerheim  *  have  reached  the  conclusion  that  fish 
oil  (tran)  does  not  hydrogenate  selectively  or  by  stages,  that  is  to  say, 
the  more  highly  unsaturated  components  do  not  largely  take  up  hydro- 
gen before  olein  becomes  converted  into  stearin.  A  certain  percentage 
of  the  highly  unsaturated  fatty  acids  remain  even  after  a  large  propor- 
tion of  the  oleic  acid  has  been  transformed  into  stearic  acid.  The  inner 
iodine  number  (iodine  number  of  the  liquid  fatty  acids)  of  a  sample  of 
hardened  tran  was  found  to  be  107,  which  result  led  to  the  foregoing 
conclusion. 

Ellis  f  effects  a  constant  circulation  and  contact  of  the  hydrogen 
gas  in  accordance  with  the  method  shown  by  Fig.  24.  The  tank  A 
contains  a  body  oil  0,  the  space  above  the  oil  being  filled  with  hydro- 
gen under  any  suitable  pressure.  The  tank  is  heated  by  the  jacket  S. 
A  pump  P  withdraws  the  hydrogen  from  the  upper  part  of  the  tank 
and  impels  it  through  the  pipe  D  into  the  lower  part  of  the  tank.  The 
catalyzer  is  added  to  the  oil  when  the  proper  temperature  is  reached 
and  the  constant  bubbling  of  a  stream  of  hydrogen  through  the  oil 
causes  intimate  contact  between  the  reacting  elements.  After  the 


FIG.  24. 


FIG.  25. 


operation  is  completed,  the  porous  plate,  fastened  to  a  movable  stem 
in  the  upper  part  of  the  tank,  may  be  depressed  to  fit  into  the  bottom 
of  the  conical  base  so  that  when  the  oil  is  withdrawn  a  good  portion  of 
the  catalyzer  remains  without  exposure  to  the  air  and  may  be  used 
with  perhaps  a  small  addition  of  fresh  catalyzer  for  the  treatment 
of  a  succeeding  charge  of  oil. 

In  U.  S.  Patent  1,043,912,  Ellis  hydrogenates  oil  (Fig.  25)  in  the 
autoclave  A.  The  pump  P  circulates  hydrogen  gas  through  the  oil. 
The  treated  product  is  run  into  the  deodorizer  D,  where  it  is  treated 

*  Zeitsch.  f.  angew.  Chem.  1914,  No.  28,  201. 
t  U.  S.  Patent  1,059,720,  April  22,  1913. 


26  THE  HYDROGENATION  OF  OILS 

with  superheated  steam  under  diminished  atmospheric  pressure  until 
the  oil  is  freed  from  noxious  gases  or  vapors.  While  the  deodorization 
of  ordinary  cottonseed  oil,  for  example,  requires  a  temperature  from 
200°  to  300°  C.  and  a  vacuum  of  down  to  one  or  two  inches  mercury, 
the  deodorization  of  the  hydrogenated  cottonseed  oil  does  not  neces- 
sarily require  as  high  a  temperature  and  the  vacuum  "  pulled  "  may 
be  considerably  less. 

Contrary  to  the  opinion  entertained  by  many  it  does  not  appear 
needful  to  violently  agitate  the  catalyzer  primarily  for  the  purpose  of 
contacting  it  with  hydrogen.  Once  the  catalyzer  is  wetted  with  the 
oil  there  can  no  longer  be  any  actual  contact  with  the  gas.  Hydrogen 
reaches  the  catalyzer  seemingly  only  through  solution  in  the  oil.  The 
forces  of  adhesion  effectually  seal  the  catalyzer  surface  from  the  gas, 
and  no  measure  of  agitation  by  ordinary  mixing  apparatus  will  dis- 
lodge the  film  of  oil.  Of  course,  agitation  secures  the  rapid  replace- 
ment of  more  saturated  by  less  saturated  portions  of  the  oil,  but  this 
replacement,  under  certain  conditions,  may  proceed  rapidly,  simply 
by  diffusion. 

The  direct  pumping  of  hot  hydrogen  gas,  especially  if  the  latter  is 
under  considerable  pressure,  offers  some  difficulties,  and  the  apparatus 
shown  in  Fig.  20  is  designed  to  effect  a  circulation  of  the  gas  by  in- 
ductive effect. ::  The  tank  1  carries  an  inductor  2  through  which  is 
forced  oil  propelled  by  the  pump  3.  The  passage  of  the  oil  through 
the  inductor  causes  hydrogen,  which  is  supplied  to  the  upper  part 
of  the  tank,  to  be  drawn  into  the  central  vertical  pipe  and  carried  with 
the  oil  to  the  bottom  of  the  tank  when  the  gas  bubbles  through  the 
main  body  of  oil.  Thus  the  oil  which  is  being  treated  is  made  use  of 
to  circulate  the  gas. 

Another  type  of  apparatus  f  involves  circulating  hydrogen  gas  by 
means  of  an  oil  scaled  pump  which  may  be  so  arranged  as  to  permit 
the  return  of  any  hydrogen  escaping  through  the  stuffing  boxes.  Fig. 

27  shows  this  apparatus:     1  is  an  oil  treating  tank  with  gas  outlet  2, 
communicating  with  a  drier  or  purifier  3.     From  the  lower  part  of 
the  latter  a  pipe  leads  to  the  pump  4  which  is  enclosed  by  the  housing 
5,  the  space  between  pump  and  housing  being  filled  with  oil.     The 
pump  discharges  into  the  lower  part  of  the  tank  through  the  gas  dis- 
tributor 6.     A  connection  7  from  the  upper  part  of  the  housing  to  the 
tank  provides  a  vent  for  gas  escaping  from  the  pump. 

In  hydrogenating  oleic  acid  in  a  vaporized  state  Shaw  t  obtained 

*  U.  S.  Patent  to  Ellis,  1,059,720,  April  22,  1913. 
t  U.  S.  Patent  to  Ellis,  1,071,221,  Aug.  26,  1913. 
j  Seifen.  Ztg.,  1912,  713. 


METHODS  OF  HYDROGENATION 


27 


some  rather  curious  results.  As  a  hydrogcnating  apparatus  Shaw 
used  a  glass  tower,  holding  catalyzer,  the  latter  being  prepared  by  put- 
ting fragments  of  pumice  into  a  50  per  cent  solution  of  nickel  nitrate. 
The  pumice  was  heated  to  a -red  heat  in  order  to  convert  the  nitrate 

to  the  oxide  and  the  process  re- 
peated in  order  to  get  a  good 
coating.  The  material  was  then 
placed  in  the  glass  tower  and  re- 
duced by  hydrogen  at  about  300° 
C.,  reduction  taking  place  in  2  to 
3  hours.  The  tower  was  heated 
in  an  oil  bath. 

Oleic  acid  was   supplied  from 
a  distilling  flask  which  was  con- 


FIG.  26. 


FIG.  27. 


nected  with  the  tower  by  gas-tight  piping.  In  the  flask  was  inserted  a 
tube  through  which  hydrogen  could  be  introduced.  The  hydrogen  was 
generated  in  a  Kipp  apparatus,  passed  through  wash  bottles  contain- 
ing nitric  acid  and  sulfuric  acid,  and  finally  through  a  "  U  "  tube 
containing  fragments  of  caustic  potash.  From  the  tower  a  delivery 
tube  extended  to  a  receiver  which  was  connected  with  a  manometer 
and  an  air  pump.  The  temperature  of  the  oleic  acid  was  maintained 
a  few  degrees  above  the  boiling  point  of  the  acid,  or  about  300°  C.  In 
this  way  the  catalyzer  was  never  wetted  with  the  liquid  acid,  but  came 
in  contact  only  with  the  gaseous  acid  which  distilled  over  from  the 
flask.  The  reaction  product  was  condensed  in  the  receiver. 


28  THE  HYDROGENATION  OF  OILS 

The  degree  of  reduction  was  determined  through  the  iodine  num- 
ber with  the  following  results:  the  iodine  number  of  oleic  acid 
employed  was  79.  When  distilled  under  a  pressure  of  100  mm.,  the 
resulting  product  had  an  iodine  number  of  75,  which  corresponds  to 
a  reduction  of  5  per  cent.  This  partially  reduced  product  under  a 
pressure  of  100  mm.  was  distilled  through  the  catalyzer,  and  the  prod- 
uct obtained  had  an  iodine  number  of  74.8,  practically  identical  with 
the  previous  value.  In  reviewing  this  unfavorable  result  it  was  con- 
cluded that  the  catalyzer  was  poisoned  and  its  activity  lost.  To  test 
this  out  a  fresh  portion  of  oleic  acid  was  distilled  through  the  catalyzer. 
Again  a  reduction  of  5  per  cent  occurred,  which  indicated  that  the 
catalyzer  was  not  poisoned. 

Distillation  at  150  mm.  was  then  tried,  giving  a  reaction  product 
having  an  iodine  number  of  68  to  70.  When  this  product  was  distilled 
again  at  150  mm.,  the  same  iodine  number  was  obtained.  A  pressure 
of  200  mm.  was  then  employed  and  the  reduction  was  20  per  cent,  while 
a  second  distillation  at  200  mm.  did  not  increase  the  amount  reduced. 

These  results  suggested  the  possibility  of  an  equilibrium  between 
stearic  acid,  oleic  acid  and  hydrogen,  and  that  the  reduction  degree 
which  Shaw  found  varied  from  pressure  to  pressure  was  constant  for 
any  one  pressure.  If  this  conclusion  were  correct,  then  the  equi- 
librium should  be  reached  from  the  opposite  end,  namely  through 
distilling  stearic  acid  in  the  presence  of  hydrogen.  In  order  to  see 
whether  this  were  possible  stearic  acid  was  treated  in  exactly  the  same 
way  as  the  oleic  acid  by  distilling  through  freshly  prepared  catalyzer. 
As  a  result  of  the  test  it  appeared  that  stearic  acid  experienced  no 
change  in  iodine  number  which  apparently  excluded  the  idea  that 
conditions  of  equilibrium  were  involved. 

Shaw's  observations  that  by  repeated  distillation  of  oleic  acid  no 
further  reduction  occurs  was  not  to  be  explained  on  the  ground  of 
fractional  distillation  of  the  partially  reduced  product,  for  the  entire 
contents  of  the  flask  were  distilled  through  the  catalyzer,  and  further- 
more the  boiling  point  of  stearic  acid  differs  very  little  from  oleic  acid, 
so  Shaw  is  at  a  loss  to  explain  the  cause  of  this  peculiar  behavior  after 
finding  it  not  due  either  to  the  existence  of  equilibrium  or  fractional 
distillation. 

An  investigation  was  made  to  determine  what  influence  length  of 
time  had  on  the  progress  of  reduction.  The  same  apparatus  was  used. 
Oleic  acid  was  distilled  under  diminished  pressure  and  the  tempera- 
ture of  the  oil  bath  maintained  at  275  degrees,  while  small  quantities 
of  the  acid  were  distilled  over  in  definite  time  intervals  and  the  iodine 
number  determined. 


METHODS  OF  HYDROGENATION  29 

The  following  is  the  result: 

2    hours  Iodine  No.  67  M.  P.  23° 

3£  hours  Iodine  No.  62  M.  P.  33° 

5    hours  Iodine  No.  60  M.  P.  37° 

9    hours  Iodine  No.  45  M.  P.  50° 

Shaw  also  determined  the  effect  of  pressure  considerably  above 
atmospheric  and  found: 

With  pressure  of  5  atmos.;  temp.  250°  C.;  Iodine  No.  77 
With  pressure  of  25  atmos.;  temp.  250°  C.;  Iodine  No.  64 
With  pressure  of  50  atmos. ;  temp.  250°  C. ;  Iodine  No.  52 

by  which  he  concludes  that  the  reduction  progresses  in  proportion  to 
the  increase  in  pressure.* 

In  the  decomposition  of  fats,  oils  and  waxes  into  fatty  acids  and 
alcohols  by  aromatic  sulfonated  fatty  acids,  the  fats  or  fatty  acids 
used  in  preparing  the  latter,  according  to  Connstein  and  von  Schon- 
than,  are  reduced  before  sulfonation,  either  by  catalytic  processes  or 
by  electrolysis.f  For  example,  castor  oil  is  hardened  by  treatment 
with  hydrogen,  using  palladium  catalyzer;  equal  parts' of  the  hardened 
product  and  naphthalene  are  mixed  and  to  the  mixture  twice  its  weight 
of  sulfuric  acid  of  66°  Baume  is  added,  avoiding  an  increase  of  tem- 
perature above  20°  C. 

The  reaction  mixture  is  stirred  until  homogeneous  and  is  then  poured 
into  somewhat  more  than  its  own  weight  of  water.  The  oily  layer 
which  separates  is  filtered  and  is  then  ready  for  use.  An  illustrative 
example  of  the  process  by  the  patentees  calls  for  treatment  of  1000 
parts  of  palm  kernel  oil,  300  parts  of  water  and  2  parts  of  the  fat 
cleavage  compound  for  6  to  8  hours  with  dry  steam.  After  separation 
of  the  two  layers  the  lower  layer  or  glycerine  water  is  concentrated 
in  the  customary  manner  while  the  upper  layer  consists  of  fatty  acids. 

According  to  Steffan  t  this  fatty  cleavage  reagent  has  been  placed 
on  the  market  under  the  name  of  "  Pfeilring."  §  Steffan  comments 
on  the  discoloring  action  of  the  Twitchell  process  on  some  fats  and  oils 
among  which  he  mentions  certain  grades  of  tallow,  soya  bean  oil  and 
fish  oil,  the  coloration  of  whose  fatty  acids  when  produced  by  the 

*  Sabatier  notes  in  his  book  on  Catalysis,  Paris,  1913,  78,  that  the  vapors  of  oleic 
acid  entrained  by  a  strong  current  of  hydrogen  and  passed  over  nickel  heated  to 
280°  to  300°  C.  are  rapidly  transformed  into  stearic  acid,  and  the  same  thing  occurs 
with  the  isomer  elaidic  acid.  (See  Ann.  Chim.  Phys.  (8),  16,  73,  1909.) 

f  British  Patent  749,  Jan.  10,  1912,  Vereinigte  Chem.  Akt.  Ges. 

J  Seifen.  Ztg.,  40,  550. 

§  " Pfeilring"  cleavage  composition  from  the  patent  standpoint  is  critically 
discussed  by  Esch  (Chem.  Rev.  u.  d.  Fett  u.  Harz  Ind.  (1913),  295). 


30  THE  HYDROGENATION  OF  OILS 

Twitchell  process  being  so  dark  that  when  made  into  soaps  the  color 
of  the  product  leaves  much  to  be  desired. 

Fat  cleavage  reagent  prepared  with  the  hardened  oil  is  claimed  to 
produce  a  much  lighter  fatty  acid.  The  rate  of  saponification  with 
the  hardened  oil  product  Pfeilring  is  approximately  that  of  the 
Twitchell  reagent.  Using  equal  parts  of  the  two  reagents  under  like 
conditions  the  following  results  were  obtained: 

5  hours,          23i  hours,         34  hours, 
per  cent  per  cent  per  cent 

Twitchell  reagent 37.23  83.31  88.94 

Pfeilring  reagent 36.92  80.18  88.69 

These  results  indicate  for  Pfeilring  a  rate  of  cleavage  slightly  less 
than  that  of  the  Twitchell  reagent,  but  it  is  brought  forward  by  the 
supporters  of  Pfeilring  that,  the  latter  reagent  being  in  itself  very  light 
colored,  while  the  Twitchell  reagent  has  a  blackish  cast,  the  propor- 
tion of  the  latter  which  may  be  used  is  limited  by  the  required  color  of 
the  resulting  fatty  acids,  but  that  Pfeilring  may  be  used  in  larger  pro- 
portion without  the  danger  of  discoloration  and  hence  the  rate  of 
cleavage  may  be  increased  by  using  a  larger  quantity  of  the  reagent 
while  the  reaction  may  be  carried  more  nearly  to  completion,  that  is 
to  95  per  cent  and  over,  without  the  discoloration  sometimes  observed 
in  the  Twitchell  process. 

In  response  to  a  critical  discussion  of  the  properties  of  soaps  made 
with  hardened  oils  *  Sudf eldt  Brothers  state  f  that  for  several  years 
they  have  been  splitting  large  quantities  of  hardened  whale  oil  by  the 
Twitchell  process  and  converting  the  fatty  acids  into  soap  and  have 
found  these  fatty  acids  to  be  of  good  color  and  the  soaps  prepared 
from  them  to  be  in  no  wise  lacking  in  color.  The  sharp  odor  noticed 
in  the  neutral  fat  is  not  lost  by  the  splitting  operation  and  also  appears 
in  the  finished  soap.J 

Reference  has  been  made  to  the  work  of  Dellemptinne  on  the  effect 
of  electrical  discharge  in  causing  the  addition  of  hydrogen  to  unsatu- 
rated  oils.  Later  work  by  this  investigator  §  furnishes  additional 
data  on  this  interesting  reaction.  The  formation  of  stearin  by  the 
action  of  an  electric  discharge  on  commercial  olein  in  an  atmosphere 
of  hydrogen  was  studied  on  both  a  small  and  large  scale.  The  appara- 
tus employed  on  a  large  scale  consists  of  a  rotatable  horizontal  axle 

*  Seifen.  Ztg.  No.  25,  1912. 
t  Seifen.  Ztg.  (1912),  720. 

J  Sudf  eldt  &  Co.  contend  in  favor  of  the  Twitchell  reagent;  Seifen.  Ztg.  (1913), 
613.     See  also  Seifen.  Ztg.  (1914),  311,  338  and  392. 
§  Bull.  Soc.  Chim.  belg.,  26,  55. 


METHODS  OF  HYDROGENATION  31 

bearing  a  large  number  of  thin,  parallel,  vertical  iron  plates  separated 
by  glass  plates,  the  former  being  connected  together  alternately  on 
opposite  sides.  The  whole  is  mounted  in  an  air-tight  iron  drum  which 
is  partially  filled  with  olein  and  into  which  hydrogen  is  introduced; 
the  odd  numbers  of  the  iron  plates  are  connected  with  one  pole  of  a 
high-potential  alternator  and  the  even  numbers  with  the  other  pole. 
When  the  axle  is  rotated,  the  electric  discharge  passes  through  a  thin 
layer  of  olcin  which  constantly  wets  the  plates.  The  glass  dielectric 
may  be  arranged  so  as  to  contact  with  one  or  both  faces  of  the  iron 
plates  (the  free  space  in  the  latter  case  being  between  the  dielectrics) 
or  the  dielectrics  may  be  separated  from  both  faces  of  the  iron  plates. 
The  capacity  of  the  largest  apparatus  constructed  was  about  1000 
pounds.  Apart  from  the  construction  of  the  apparatus  the  yield  is 
influenced  by  the  current  density,  the  frequency  of  the  current,  gaseous 
pressure,  temperature  of  the  liquid  and  the  distance  between  consec- 
utive iron  plates.  If  the  reduction  is  not  pushed  beyond  a  point  cor- 
responding to  a  15  per  cent  decrease  in  the  iodine  number,  there  is 
a  complete  parallelism  between  the  decrease  in  the  iodine  number, 
increase  of  melting  point  and  absorption  of  hydrogen.  The  varia- 
tion of  the  iodine  number  or  the  increase  of  the  melting  point  per  unit 
of  electrical  energy  employed  is  taken  as  a  measure  of  the  trans- 
formation effected.  A  proportionality  between  the  quantity  of  sub- 
stance transformed  and  the  intensity  of  current  does  not  always  exist. 
For  a  given  intensity  of  current  the  quantity  transformed  reaches  a 
maximum  for  a  definite  distance  of  electrical  discharge;  this  maximum 
varies  with  the  pressure.  In  order  to  obtain  a  satisfactory  reaction 
the  current  must  act  simultaneously  on  both  liquid  and  gas.  Pro- 
longed action  of  the  current  causes  polymerization  and  the  reactions 
become  quite  complicated.  The  apparatus  can  be  used  for  deodoriz- 
ing fish  oil,  as  the  unsaturated  compounds  of  this  oil  take  up  hydrogen 
under  these  conditions.  Because  of  the  gradual  polymerization  pro- 
duced the  method  is  suggested  as  applicable  for  thickening  mineral 
oils  or  mixtures  of  mineral  oils  with  animal  or  vegetable  oils.  Molec- 
ular weights  as  high  as  2500,  as  determined  by  the  ebullioscopic 
method,  were  obtained.  The  viscosity  of  these  polymerized  oils  varies 
less  with  the  temperature  than  does  that  of  the  pure  mineral  oils;  the 
coefficient  of  friction  of  the  former  is  also  stated  to  be  less. 

Apparatus  patented  by  Hemptinne  *  is  of  the  following  character: 
A  series  of  parallel  rotatable  metal  plates,  with  discs  of  insulating 
material  between  adjacent  plates,  is  arranged  within  a  fixed  casing 
or  within  a  vessel  that  rotates  with  the  plates  on  a  horizontal  axis. 

*  British  Patent  7101,  April  4,  1905. 


32 


THE  HYDROGENATION  OF  OILS 


Alternate  metal  plates  are  connected  to  one  pole,  and  the  remainder 
to  the  other  pole  of  a  source  of  electric  current,  in  order  to  establish  a 
silent  electric  discharge  between  the  plates.  The  latter  are  partially 
immersed  in  the  absorbing  liquid,  which  is  carried  around  by  small 
troughs  attached  to  the  casing  and  delivered  on  to  the  upper  portions 
of  the  plates,  so  that  a  thin  layer  of  liquid  is  maintained  on  the  plates, 
and  the  gas  to  be  treated  is  thus  brought  into  intimate  contact  with 
the  liquid.  An  electro-magnetic  device,  working  automatically,  main- 
tains a  constant  pressure  of  gas  in  the  apparatus  during  the  absorption.* 

A  process  for  the  production  of  neutral  hydrogenated  fats  from  raw 
material  containing  fatty  acid  involves  hydrogenating  the  oil  in  the 
presence  of  glycerine  under  which  condition  the  fatty  acids  are  claimed 
to  be  converted  into  glycerides.f 

With  an  apparatus  as  shown  in  Fig.  28,  Ellis  ±  hydrogenates  by 
passing  a  current  of  oil  through  a  rotary  drum  containing  catalytic 


FIG.  28. 


material  supported  on  coarse  fragments  of  pumice,  so  that  on  rota- 
tion of  the  drum  the  catalyzer  moves  in  a  direction  substantially 
transversely  to  the  direction  of  the  oil  current.  Hydrogen  may  be 
passed  through  the  drum  as  a  counter-current.  A  given  quantity 
of  oil  may  be  circulated  in  this  manner  until  hardened  to  the  requisite 
degree.  § 

*  The  application  of  the  electric  current  in  the  industry  of  oils  and  fats  has  been 
reviewed  by  Buttlar  (Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1912),  97)  who  discusses 
its  use  in  the  transformation  of  liquid  oils  into  solid  fats,  also  in  the  bleaching  of 
oils. 

f  Seifen.  Ztg.  (1913),  263. 

t  U.  S.  Patent  1,052,469,  Feb.  11,  1913. 

§  In  U.  S.  Letters  Patent  1,095,144  of  April  28,  1914,  to  Ellis  a  process  is  set 
forth  for  hardening  oils  which  involves  the  movement  of  oil  and  catalyzer  in  a  direc- 
tion transverse  to  that  of  the  hydrogen  current. 


CHAPTER  II 
METHODS   OF  HYDRO  GEN  ATION  —  Continued 

Utescher  *  treats  oils  with  hydrogen  in  presence  of  a  finely-divided 
catalytic  agent,  and  at  the  same  time  the  material  is  subjected  to  the 
action  of  a  silent  electric  discharge.!  In  a  description  of  the  process, 
it  is  stated  that  the  "  silent  discharge"  is  prevented  from  coming  into 
actual  contact  with  the  fatty  substance,  only  chemically  active  rays 
(e.g.  from  a  mercury  vapor  lamp)  being  utilized.  It  is  also  stated 
that  the  process  may  be  effected  by  allowing  the  rays  to  impinge  on 
the  surface  of  a  catalytic  substance,  which  may  be  used  in  the  form 
of  plates.  J 

The  joint  application  of  a  catalytic  and  an  electric  discharge  is 
claimed  to  give  a  greater  effect  than  either  agent  singly.  § 

Some  observations  on  the  effect  of  ultra-violet  light  on  catalytic 
action  have  been  made  by  Farmer  and  Parker  ||  which  indicate  that 
on  colloidal  platinum,  at  least,  the  ultra-violet  light  exerts  a  retarding 
influence  on  the  rate  of  catalytic  change.  Colloidal  platinum  was 
prepared  by  the  Bredig  method,  i.e.,  by  producing  an  arc  between 
platinum  electrodes  under  distilled  water.  Hydrogen  dioxide  was 
used  as  a  measure  of  catalytic  activity.  The  colloidal  platinum  was 
exposed  to  the  ultra-violet  light  and  samples  were  drawn  from  time 
to  time  in  order  to  get  exposures  of  varying  lengths,  the  samples  being 
introduced  into  hydrogen  peroxide  placed  in  an  apparatus  shown  in 
Fig.  29.  The  inclined  tube  of  this  apparatus  was  completely  filled 
with  dilute  hydrogen  peroxide  solution  and  a  bent  delivery  tube 
arranged  to  collect  any  liquid  displaced.  As  colloidal  platinum  breaks 

*  British  Patent  20,061,  Sept.  3,  1912. 

t  Hydrogen  activated  by  actinic  rays  is  used  for  oil  hardening  (Seifen.  Ztg.  (1913), 
1298). 

t  In  this  connection  it  is  noted  that  the  text  of  the  Utescher  specification  of 
German  Patent  266,662  of  1912  appears  in  Chem.  Rev.  u.  d.  Fett  u.  Harz  Ind.  (1913), 
308. 

§  Seifen.  Ztg.  (1913),  851.  F.  Gruner,  French  Patent  453,664,  Jan.  27,  1913.  Oils 
or  fats  are  subjected  to  the  action  of  a  silent  discharge  of  an  electric  current  of  very 
high  tension  and  frequency.  Currents  of  high  potential  (50,000  to  100,000  volts) 
and  high  frequency  are  employed. 

II  Jour.  Am.  Chem.  Soc.  (1913),  1524. 

33 


34 


THE  HYDROGENATION  OF  OILS 


FIG.  29. 


down  hydrogen  dioxide  yielding  oxygen,  the  evolution  of  the  gas  and 

consequent  displacement  of  liquid 
enabled  the  rate  of  decomposition 
to  be  measured. 

The  experiments  showed  that 
the  catalytic  activity  of  the  col- 
loidal platinum  was  almost  com- 
pletely destroyed  after  an  exposure 
of  six  hours,  the  activity  then  ob- 
served being  no  greater  than  that 
of  the  spontaneous  decomposition 
of  hydrogen  peroxide  itself.  It 
was  noted  that  the  light  caused 

the  platinum  to  be  precipitated  out  of  solution  as  a  black  flocculent 

material.     After  such  a  precipi- 
tation it  was  in  the  form  of  large 

mossy  clusters. 

While   no    observations   were 

made  with  respect   to   the   hy- 

drogenation  of  oils  under  these 

conditions,  in  view  of  the  action 

of  ultra-violet  light  on  solutions 

of  colloidal  platinum,  it  would 

appear    that    exposure    thereto 

may  be  expected  to  modify  the 

rate  of  reaction  in  the  harden- 
ing of  oils.* 

A    process   of    hydrogenating 

oils  involving  exposure  of  the  oil 

as  a  thin  film  on  a  web  carrying 

catalytic  material  has  been  pro- 
posed by  Walter.f   Fig.  30  shows 

one  form  of  apparatus  described 

by  Walter  for  carrying  out  this 

reaction.    A  is  a  closed  vessel  in  pIG   30. 

which  is  placed  a  belt  or  web 

B  carrying  catalytic  material.     The  belt  may  be  made  of  asbestos 

or  cotton  cloth  and  may  be  impregnated  with   platinum,   iridium, 

*  Some  preliminary  experiments  by  the  author  point  to  a  reduction  in  the  iodine 
number  of  cottonseed  oil  when  exposed  to  ultra-violet  light  in  an  atmosphere  of 
hydrogen. 

t  Seifen.  Ztg.  (1913),  442. 


METHODS  OF  HYDROGENATION 


35 


nickel  or  other  catalytic  material.  The  belt  is  carried  on  rollers  E, 
one  of  which  dips  into  the  oil.  Catalyzer  also  may  be  carried  in 
the  container  C  attached  to  the  belt  B.  D  is  a  steam  or  water  bath. 
H  is  an  inlet  and  F  an  outlet  for  hydrogen.  0  is  an  inlet  for  oil. 

Two  other  types  of  apparatus 
are  described:  one  consists  of  an 
upright  stationary  cylinder  jack- 
eted for  about  one-half  the  dis- 
tance. The  interior  has  a  shaft 
with  4  arms  upon  which  the 
catalyzer  is  carried  and  revolved 
through  the  liquid  and  gas.  A 
bucket  arrangement  is  also  at- 
tached to  the  shaft  to  throw 
liquid  upon  the  catalyzer.  An- 
other type  consists  of  a  jacketed 
horizontal  cylinder  with  a  rotating 
shaft  supporting  arms  for  carrying 

the  catalyzer.     (Figs.  31,  32  and  FlG   31 

33.) 

The  operation  may  be  carried  out  with  the  aid  of  chemically-active 
light  for  which  purpose  a  lamp-lighting  system  of  actinic  character 

is  shown  at  L  positioned  in  the 
receptacle  A.  Walter  lays  great 
stress  on  the  rapid  absorption  of 
hydrogen  by  oil  or  other  material 
exposed  in  this  manner  in  thin 
films.  He  states  that  although 
the  film  of  oil  on  the  belt  covers 
the  catalyzer,  and  in  consequence 
one  would  expect  the  reaction  to 
be  hindered  by  the  sealing  effect 
of  such  a  film,  yet  the  liquid  and 
gas  react  very  quickly  with  one 
another.  The  solubility  of  the  gas 
in  the  liquid,  as  well  as  the  physical 
properties  of  the  latter,  he  states, 
do  not  appear  to  play  any  essential 
part,  for  the  sparingly  soluble  hydrogen  exerts  its  reducing  action 
apparently  just  as  quickly  in  a  thinly-fluid  alcoholic  quinine  solution 
as  it  does  in  a  viscous  fish  oil. 

Walter  recommends  passing  the  oil  through  a  series  of  receptacles 


FIG.  32. 


36 


THE  HYDROGENATION  OF  OILS 


containing  catalyzer  attached  to  a  belt  as  described  or  to  an  agitator 
arm,  the  arrangement  being  such  that  the  oil  first  enters  the  receptacle 

which  contains  the  weakest  or  more  nearly 
spent  catalyzer  and  after  short  treatment 
passes  to  the  next  container  and  so  on  until 
finally  it  reaches  the  last  receptacle  where 
the  most  active  catalyzer  is  employed. 

In  connection  with  the  above  it  may 
be  stated  that  Walter  has  been  granted 
German  Patent  257,825,  of  July  27,  1911, 
which,  in  brief,  has  to  do  with  the  produc- 
tion of  chemical  reactions  between  liquids 
and  gases  under  the  influence  of  a  contact 
substance  or  of  chemically-active  rays. 
Porous  or  roughened  bodies,  which  may 
serve  as  contact  substances,  are  supported 
on  movable  carriers  and  are  caused  alter- 
nately to  dip  into  the  liquid  and  then  rise 
into  the  gas  above  the  liquid,  so  as  to 
bring  fresh  quantities  of  the  liquid  con- 
tinually into  contact  with  the  gas,  over  a 
large  surface.  Several  reaction  chambers 
through  which  the  gas  and  liquid  pass  in 
a  definite  order  are  preferably  used.  In 
some  respects  this  resembles  the  process 
of  Kayser  previously  discussed. 

Birkeland  and  Devik  *  employ  a  form  of  apparatus  which  permits 
of  forcing  a  mixture  of  oil  and  catalytic  agent  downwards  through  a 
nozzle  into  an  atmosphere  of  hydrogen,  filling  the  space  above  the 
bulk  of  the  oil,  which  is  contained  in  an  autoclave.  The  hydrogen 
is  drawn  into  the  oil  jets  by  injector  action  and  subsequently  rises  in 
small  bubbles  through  the  body  of  oil.  The  process  is  preferably 
carried  out  under  a  pressure  of  10  to  15  atmospheres  and  at  a  tem- 
perature of  about  150°  C.  Sudden  reduction  of  the  pressure  is  claimed 
to  promote  the  hydrogenation  of  the  oil. 

Brochet  f  treats  unsaturated  compounds  as  a  class,  by  hydrogen, 
in  the  presence  of  a  catalyst.  Hydrogen  or  a  gaseous  mixture  con- 
taining hydrogen  is  passed  into  the  substance  to  be  treated,  either  in 
the  liquid  form  or  in  solution  or  suspension,  in  presence  of  a  base- 


FIG.  33. 


*  French  Patent  456,632,  April  14,  1913. 
t  French  Patent  458,033,  July  27,  1912. 


METHODS  OF  HYDROGENATION  37 

metal  catalyst,  which  may  be  held  on  an  inert  support.     The  velocity 
of  the  reaction  is  increased  by  working  under  pressure,   although 
extremely  high  pressures  are  not  necessary.     By  this  procedure  various 
unsaturated    organic    compounds    may   be    made   to   combine   with- 
hydrogen.* 

A  somewhat  elaborate  gas-measuring  system  has  been  proposed  by 
deKadt.f  The  amount  of  gas  absorbed  by  a  liquid  or  other  material 
in  a  closed  vessel,  for  example,  in  the  combination  of  hydrogen  with 
fats  or  oils  in  the  presence  of  a  catalyst,  is  determined  by  means  of  a 
gas  meter  or  other  measuring  instrument  arranged  on  the  pipe  sup- 
plying the  gas  and  adapted  to  cut  off  the  supply  when  a  certain  amount 
of  gas  has  been  supplied  or  combined.  When  apparatus  is  used  in 
which  the  g^s  is  introduced  through  a  fine-spray  nozzle  at  the  bottom 
of  the  liquid,  and  unabsorbed  gas  from  the  top  of  the  vessel  is  with- 
drawn and  again  introduced  into  the  liquid,  two  meters  are  fitted  upon 
the  inlet  and  outlet  pipes  respectively  so  as  to  act  differentially  upon 
an  indicator  needle  which  thus  records  the  difference  between  the 
volume  of  gas  supplied  and  the  volume  unabsorbed.  The  needle 
may  control  an  electric  contact  by  which  the  gas  supply  is  shut  off 
and  the  circulating  pump  stopped  as  soon  as  the  requisite  amount  of 
gas  has  been  absorbed. 

Fig.  34  shows  the  deKadt  system. 

The  reaction  vessel  1  is  connected  at  its  upper  part  through  a  suitable  pipe  con- 
nection 2  with  a  suction  and  force  pump  3.  At  one  part  of  its  length  this  pipe  con- 
nection 2  is  formed  into  a  cooling  coil  4,  which  is  located  in  a  water  reservoir  5.  At 
the  lower  part  of  the  reaction  vessel  1  a  nozzle  or  rose  head  6  is  provided,  and  from 
this  nozzle  a  pipe  7  leads  to  the  vessel  8  containing  the  hydrogen.  This  hydrogen- 
containing  vessel  communicates  with  the  pump  3  by  means  of  a  pipe  9  and  contains 
a  cooling  coil  12  provided  with  inlets  and  outlets  for  the  supply  and  discharge  of 
the  cooling  water. 

The  material  to  be  treated,  such  as  fats  or  oils,  and  the  catalytically  acting  sub- 
stances are  supplied  to  the  reaction  vessel  through  a  charging  door  14.  In  the  first 
place  the  hydrogen  supply  pipe  7  is  cut  off  from  the  reaction  vessel  1  and  the  pipe  9, 
connecting  the  hydrogen-containing  vessel  with  the  pump,  is  closed  by  a  cock  15. 
The  materials  contained  in  the  reaction  vessel  are  then  heated  by  means  of  a  steam 
jacket  or  steam  coil,  and  the  air,  contained  in  this  vessel,  is  exhausted  by  means  of 
the  pump  3  and  escapes  to  the  atmosphere  by  way  of  the  cock  16,  the  cocks  18 
and  17  being  open  for  this  purpose.  Hydrogen  is  then  supplied  through  a  pipe 
connected  with  the  pump  3  and  is  forced  into  the  hydrogen-containing  vessel  8 
through  the  pipe  9,  the  cocks  17  and  15  being  open.  When  the  necessary  tension 
has  been  attained,  the  cocks  15  and  17  in  the  hydrogen  supply  pipe  arc  closed  and 
the  cock  24  at  the  upper  part  of  the  reaction  vessel  connecting  the  vessel  and  pipe  2 
are  opened.  A  valve  19  is  arranged  in  the  pipe  connecting  the  hydrogen  vessel  with 

*  See  also  First  Addition  dated  Oct.  8,  1912. 
t  British  Patent  5773,  March  7,  1912. 


38 


THE  HYDROGENATION  OF  OILS 


the  lower  part  of  the  reaction  vessel  by  opening  said  valve  19,  behind  which  a 
reducing  valve  20  is  arranged;  the  hydrogen  is  conducted  by  the  pipe  7  into  the 
vessel  1,  where  it  passes  from  the  nozzle  6  through  the  material  to  be  treated  with 
which  it  combines  to  some  extent,  while  the  excess  escapes  upwards  and  is  again 
forced  into  the  hydrogen-containing  vessel  8  by  the  pump  3,  the  cocks  being  suitably 
adjusted.  The  supply  of  hydrogen  contained  in  the  vessel,  which  is  not  supple- 
mented by  a  fresh  external  supply  during  the  chemical  reaction,  must  gradually 
decrease  in  tension  owing  to  the  combination  with  the  contents  of  the  reaction 
vessel.  This  decrease  in  tension  can  be  utilized  empirically  for  determining  the 
progress  of  the  chemical  reaction  or  for  ascertaining  its  various  stages  or  its  com- 
pletion. These  indications  would,  however,  only  be  approximate  and  deKadt 
therefore  provides  means  to  interrupt  the  supply  of  hydrogen  to  the  reaction  vessel 
automatically  after  the  consumption  of  the  necessary  quantity  of  combined  hy- 
drogen. 


FIG.  34. 


With  this  object  a  gas  meter  21  is  arranged  on  the  pipe  7  supplying  the  hydrogen 
to  the  reaction  vessel  and  indicates  the  quantity  of  hydrogen  passing  from  the 
container  8  into  the  reaction  vessel  1.  A  similar  meter  22  is  arranged  on  the 
return  pipe  2  and  measures  the  quantity  of  gas  being  withdrawn.  Both  these 
meters  act  on  an  indicating  shaft  23  in  such  a  manner  that  by  the  rotation  of  the 
shaft  the  first  gas  meter  21  moves  the  hand  of  indicating  shaft  23  upwards,  while 
the  other  gas  meter  22  moves  it  rearwards  so  that  the  index  hand  shows  the  differ- 
ence, that  is  to  say  the  consumption  of  hydrogen.  An  electric  contact  is  arranged 
in  the  path  of  the  index  hand  and  when  it  reaches  a  certain  position,  in  which  the 
necessary  quantity  of  hydrogen  has  been  consumed,  the  circuit  is  closed,  and  the 
hydrogen  supply  is  cut  off. 

In  hydrogenating  oils  containing  the  hydroxyl  group,  at  high  tem- 
peratures, this  group  is  destroyed  and  Markel  and  Crosfield  *  propose 

*  British  Patent  13,519,  June  6,  1911. 


METHODS  OF  HYDROGENATION  39 

the  preparation  of  saturated  hydroxy-fatty  acids  and  their  glycerides 
by  treating  the  corresponding  unsaturated  acids  or  glycerides  with 
hydrogen  in  the  presence  of  a  catalyst  other  than  palladium  and  pal- 
ladium hydroxide,  at  as  low  a  temperature  as  possible,  preferably 
just  above  the  melting  point  of  the  final  product,  in  order  to  avoid 
splitting  off  of  the  hydroxyl  group  or  to  control  such  splitting  to  any 
desired  extent.  Suitable  catalysts  recommended  are  iron,  nickel, 
cobalt,  copper,  etc.,  also  oxides,  hydroxides  and  salts,  which  may  be 
deposited  upon  suitable  supports,  preferably  finely  divided.  As  raw 
materials  the  mixture  of  unsaturated  acids  obtained  by  treatment  of 
oleic  acid  with  sulfuric  acid,  the  oxidation  products  of  linseed,  cot- 
tonseed and  rape  oils,  also  castor,  grape  seed  and  whale  oils  may  be 
used. 

Temperature  of  Hydrogenation.  For  each  compound  there  usually 
exists  a  well-defined  range  of  temperature  within  which  hydrogen  is 
effectively  added.  Somewhere  in  this  temperature  interval  lies  the 
mean  effective  temperature,  that  is  the  temperature  of  maximum  sat- 
uration velocity.  For  a  number  of  fatty  oils  this  approximates  180°  C. 
or  356°  F.  with  a  nickel  catalyzer.  As  a  rule  hydrogenation  is  accel- 
erated more  by  a  given  temperature  rise  from  below  the  mean  effective 
temperature  than  the  same  temperature  increase  above  this  point  re- 
tards the  reaction.  For  example,  raising  the  temperature  from  170° 
to  180°  C.  increases  the  rate  of  hydrogen  addition  in  a  certain  measure 
while  elevating  the  temperature  from  180°  to  190°  C.  retards  the  rate, 
but  to  a  lesser  degree  for  such  10-degree  temperature  increment  than 
the  previous  increase  in  the  rate.  In  operation  on  the  large  scale  it 
is,  therefore,  better  to  err  by  maintaining  the  oil  slightly  above  rather 
than  below  the  mean  effective  temperature,  unless  of  course  a  lower 
temperature  is  prescribed  because  of  the  character  of  the  oil.  Rapidity 
of  treatment  often  is  desired  especially  in  edible  oils  where  protracted 
contact  with  the  catalyzer  introduces  the  danger  of  solution  of  the 
metallic  material  in  the  oil  to  an  objectionable  degree.* 

The  range  of  temperature  mentioned  above  varies  with  each  type 
of  catalyzer.  Platinum  and  palladium,  at  least  in  certain  forms,  may 
be  used  at  temperatures  between  80°  and  100°  C. ;  nickel  between 
160°  to  200°  C. ;  nickel  oxide  and  copper  at  about  200°  C.  and  upwards; 

*  The  hydrogenation  of  unsaturated  compounds,  particularly  fatty  acids  and 
their  glycerides,  into  saturated  compounds  by  hydrogen  in  the  presence  of  finely- 
divided  metal,  according  to  Higgins  is  accelerated  by  the  presence  of  formic  acid 
or  other  volatile  organic  acid.  The  formic  acid  may  be  carried  by  the  hydrogen, 
or  the  acid  mixed  with  the  material  before  treatment.  (Chem.  Abs.  (1914), 
437.) 


40  THE  HYDROGENATION  OF  OILS 

all  depending  on  the  physical  and  chemical  constitution  of  the  catalytic 
material.* 

Caro  f  considers  the  presence  of  carbon  monoxide  in  hydrogen  used 
for  hardening  fats  with  nickel  catalyzers  to  be,  under  some  circum- 
stances, injurious  to  the  catalyzer.  Maintaining  the  temperature  of 
the  oil  during  hydrogenation  above  200°  C.  is  said  to  be  beneficial  as 
any  nickel  carbonyl  formed  will  be  at  once  decomposed  at  that  tem- 
perature. The  hydrogenation  of  many  substances  under  these  con- 
ditions is  not  feasible  and  Caro  recommends  that  the  gas  first  be  passed 
over  nickel  at  180°  C.  to  convert  the  carbon  monoxide  into  methane, 
which  is  inert. 

DeKadt  J  saturates  fatty  acids  or  their  esters  with  hydrogen  by  the 
use,  as  a  catalyzer,  of  a  soap  of  a  heavy  or  noble  metal,  formed  from 
a  fat  or  fatty  acids,  whose  melting  point  lies  above  that  of  the  sub- 
stance to  be  treated.  § 

It  is  claimed  by  Fuchs  ||  that  his  investigations  have  shown  the 
present  methods  of  reduction  for  the  most  part  are  improperly  founded, 
causing  long  duration  of  time  of  treatment  coupled  with  marked  loss 
of  hydrogen  and  heat;  use  of  a  great  excess  of  hydrogen  or  catalyzer; 
injurious  action  of  the  long  heating  on  the  color,  taste  and  odor  of 
the  reduced  fat;  and  the  application  of  high  pressure  in  apparatus 
which  involves  costly  autoclaves,  dangerous  to  handle.  Fuchs  de- 
clares that  the  conduct  of  reduction  of  fatty  bodies  is  essentially 
improved  if  the  following  theoretical  conditions  are  observed: 

(1)  Thermal  considerations:  A  quickening  of  the  reaction  is  ob- 
tained when  the  oil  to  be  treated  is  maintained  at  only  a  moderate 
temperature  (0°  to  150°  C.),  while  the  hydrogen  employed  is  heated 
to  200°  to  250°  C.  The  avoidance  of  strong  heating  of  the  oil  which 
is  being  treated  is  favorable  to  the  quality  of  the  final  product,  while 
preheating  the  hydrogen  appears  to  increase  its  activity.  Compara- 
tive tests  show  that  in  this  way  the  speed  of  the  reaction  can  be  in- 
creased by  about  10  per  cent.  For  preheating  the  current  of  gas, 
copper  or  nickel  coils  in  an  oil  bath  are  used.  The  oil  bath  may  be 

*  Ipatiew  (Chem.  Ztg.,  1914,  374)  has  noted  that  the  hydrogenation  of  fatty 
acids  with  metallic  nickel  begins  at  150°  C.  and  with  nickel  oxide  at  230°  C.  The 
reaction  progresses  readily  at  both  high  and  low  pressures. 

t  Seifen.  Ztg.  (1913),  852. 

J  Chem.  Ztg.  Rep.  (1913),  541,  British  Patent  18,310,  Aug.  9,  1912. 

§  Utescher  (Seifen.  Ztg.  (1912),  1044)  discusses  from  the  patent  point  of  view  the 
claims  made  by  deKadt  in  Seifen.  Ztg.  (1912),  960;  see  also  Seifen.  Ztg.  (1912),  900 
and  1008. 

II  Seifen.  Ztg.  (1913),  982.  Reduction  of  unsaturated  fatty  acids  and  their 
glycerides,  Belgium  Patent  256,574,  1913. 


METHODS  OF  HYDROGENATION  41 

maintained  at  the  requisite  temperature  through  circulation  of  oil 
heated  at  a  distant  point. 

(2)  Chemical  considerations:  Since  it  is  impossible  to  have  free 
hydrogen  in  its  most  active  form,  that  is,  in  a  nascent  state,  act  upon 
the  oil  to  be  treated,  because  the  quality  of  the  oil  is  injured,  Fuchs 
observes  that  means  must  be  provided  to  apply  the  hydrogen  in 
the  atomic  form.  This  can  be  carried  out  through  the  application 
of  chemically  active  rays.  Dissociation  of  the  hydrogen  molecule 
appears  also  to  occur  when  molecular  hydrogen  is  passed  over  cata- 
lytic material  such  as  palladium  black  or  freshly  prepared  nickel 
powder  and  then  is  allowed  to  diffuse  under  high  pressure  through 
heated  plates  of  metal.  The  activity  of  the  dissociated  hydrogen, 
it  is  claimed,  is  from  15  to  20  per  cent  higher  than  the  normal  gas. 
The  catalytic  material  may  be  placed  in  a  tube  of  suitable  length  or 
on  the  plates  of  a  column  apparatus.  By  way  of  illustration  Fuchs 
states  thai  cottonseed  oil  carrying  0.9  per  cent  of  a  catalyzer,  prepared 
from  nickel  carbonate,  is  raised  to  a  temperature  of  120  degrees  and 
is  subjected  to  hydrogen  under  a  pressure  of  18  atmospheres,  the  gas 
having  been  chemically  activated  by  passage  through  an  iron  tube 
3  meters  in  length  and  60  mm.  in  diameter,  lined  with  platinized 
asbestos  and  heated  to  250°  C.  In  this  way  by  two  hours'  treatment 
a  fatty  body  having  a  melting  point  of  44°  C.  was  prepared.  In  three 
hours  a  fat  melting  at  65.4°  C.  was  obtained.  Fuchs  notes  that  ordi- 
narily from  5  to  8  hours  would  be  required  to  secure  such  products. 
The  claims  of  Fuchs7  Patent  call  for  the  reduction  of  unsaturated 
fatty  acids  and  their  glycerides  by  means  of  hydrogen  according  to 
the  contact  process,  wherein  strongly  heated  hydrogen  is  caused  to 
react  on  only  moderately  heated  oil;  also  the  treatment  of  oil  with 
atomic  hydrogen  whose  activity  has  been  increased  by  treatment  with 
chemically  active  rays. 

The  employment  of  nickel  carbonyl  by  Shukoff  has  been  described 
in  the  foregoing.  In  a  somewhat  similar  manner  Lessing  *  makes  use 
of  a  mixture  of  hydrogen  and  a  gaseous  metallic  compound  brought 
into  contact  with  the  substance  under  suitable  conditions  of  tempera- 
ture and  pressure.  Lessing  states  he  has  found  thfit  a  great  number 
of  substances  may  be  hydrogenated  by  treating  them  at  elevated 
temperatures  with  hydrogen  to  which  a  metallic  carbonyl  vapor,  or 
gas  containing  a  metallic  carbonyl,  has  previously  been  added;  or 
with  a  mixture  of  gases,  containing  hydrogen  in  which  metal  carbonyl 
has  been  formed  by  combination  of  carbon  monoxide,  originally  in 
the  mixture,  with  a  metal.  The  rapidity  with  which  the  hydrogena- 
*  British  Patent  18,998,  1912. 


42  THE  HYDROGENATION  OF  OILS 

tion  proceeds  under  these  conditions  may  be  explained  as  the  effect 
of  the  liberation  of  elementary  metal,  the  properties  of  which  "  in 
statu  nascendi  "  are  known  to  be  very  different  from  those  of  metal 
which  is  merely  finely  subdivided.  Lessing  observes  that  it  has 
already  been  proposed  to  use  as  the  catalyzer  finely-subdivided  nickel, 
made  by  decomposing  nickel  carbonyl  in  the  heated  material  prior 
to  the  introduction  of  the  hydrogenating  gas,  but  it  was  not  known 
that  technical  advantages  accrue  from  conveying  the  nickel  carbonyl 
into  the  material  simultaneously  with  the  hydrogenating  agent  so 
that  elementary  liberation  of  nickel  occurs  in  close  contact  with  hydro- 
gen and  the  substance  to  be  hydrogenated.  These  advantages  are 
that  the  proportion  of  catalyzer  is  very  much  reduced  and  the  reaction 
proceeds  much  more  rapidly.  Lessing  carries  out  his  process  in 
various  ways.  It  is  convenient  to  introduce  nickel  carbonyl  into  the 
hydrogen  gas  by  passing  a  mixture  of  the  latter  with  carbon  monoxide 
over  reduced  nickel  in  the  well-known  manner  for  making  nickel 
carbonyl. 

The  mixture  of  gases  employed  need  not  be  of  great  purity  and  may  be  made  from 
water-gas,  or  by  the  thermal  decomposition  of  coal  gas  or  of  coke-oven  gas  or  of 
hydrocarbons  of  any  kind,  but  best  results  are  obtained  when  the  amount  of  carbon 
monoxide  in  the  gases  is  limited  to  that  requisite  for  forming  the  nickel  carbonyl 
necessary  for  the  reaction,  and  in  any  case  the  proportion  of  carbon  monoxide  in 
the  mixture  should  not  exceed  25  per  cent.  For  example,  when  an  oil  such  as  a 
glyceride  or  a  fatty  acid  is  being  hydrogenated,  the  simplest  mode  of  operating  con- 
sists in  passing  hydrogen  containing  5  to  10  per  cent  of  carbon  monoxide  first  through 
a  volatilizer  charged  with  reduced  nickel  and  then  through  the  oil  contained  in  a 
closed  vessel  heated  to  a  suitable  temperature,  say  from  200°  to  240°  C.  The  gases 
passing  away  from  the  vessel  are  returned  to  the  volatilizer  to  be  used  again,  hydro- 
gen or  a  gas  rich  therein  being  added  to  compensate  for  that  absorbed  by  the  oil. 
The  proportion  of  nickel  required  for  the  hydrogenation  is  very  small;  under  proper 
conditions  excellent  results  can  be  obtained  with  a  proportion  equivalent  to  0.1  part 
of  nickel  to  100  parts  of  oil. 

Another  mode  of  operating  consists  in  forcing  the  substance  to  be  treated,  if  it 
is  in  a  liquid  form,  through  spraying  nozzles  into  a  gas-tight  vessel  which  may  be 
suitably  heated  to  the  temperature  most  favorable  to  the  catalytic  hydrogenation 
of  the  substance.  Into  the  same  container,  preferably  at  or  near  the  bottom,  hydro- 
gen gas  containing  i^tal  carbonyl,  for  instance  nickel  carbonyl,  is  passed.  The 
excess  of  gases  leaves  the  vessel  through  an  outlet  at  the  upper  part  and  may  be 
returned  into  the  gas  circuit  after  the  products  carried  with  it  have  been  separated 
by  condensing  or  washing.  The  treated  liquid  may  be  drained  off  and  returned  to 
the  reaction  vessel  until  hydrogenation  has  proceeded  far  enough.  Instead  of  heat- 
ing the  reaction  vessel,  or  in  addition  to  doing  so,  the  liquid  may  be  preheated  in 
a  suitable  apparatus,  before  entering  the  vessel,  to  a  temperature  required  for  the 
reaction. 

By  another  method  of  carrying  out  the  process,  a  solution  of  metal  carbonyl  in 
oil  is  prepared,  which  may  be  accomplished  by  passing  the  gas  carrying  nickel  car- 


METHODS  OF  HYDROGENATION  43 

bonyl  through  cold  oil.     This  solution  is  forced  through  a  spray  nozzle  into  a  heated 
vessel  where  it  meets  hydrogen  whereupon  hydrogenation  occurs. 

If  the  compound  to  be  treated  is  in  the  state  of  gas  or  vapor,  as  for  instance  in 
the  hydrogenation  of  the  more  volatile  tar  oils,  it  is  simply  mixed  with  hydrogen 
containing  the  nickel  carbonyl  and  is  subjected  to  the  temperature  required  for 
hydrogenation.  Likewise  in  the  case  of  a  liquid  some  hydrogen  may  be  mixed  with 
the  liquid,  the  spray  being  then  preferably  formed  by  injector  action  instead  of  by 
liquid  pressure. 

The  use  of  nickel  carbonyl  for  the  production  of  catalytic  material 
also  has  been  patented  by  Kamps,*  who  introduces  the  carbonyl  into 
an  autoclave  at  a  temperature  above  43°  C.  and  a  pressure  of  751  mm., 
and  the  oil  which  is  to  be  reduced  is  maintained  under  such  pressure 
and  temperature  conditions  that  the  decomposition  of  the  nickel 
carbonyl  is  brought  about.  At  60°  C.  the  oil  should  be  under  a 
pressure  of  less  than  2  atmospheres  and  at  180°  C.  less  than  30  at- 
mospheres. 

Another  method  of  utilizing  nickel  carbonyl  for  the  production  of 
catalytic  material  is  that  proposed  by  the  Bremen  Besigheimer 
Olfabriken  |  according  to  which  method  kieselguhr  or  similar  porous 
material  is  saturated  with  nickel  carbonyl  and  the  material  is  heated 
to  cause  the  deposition  of  metallic  nickel  on  the  carrier.  The  nickel- 
containing  powder  is  immediately  ground  with  oil  to  form  a  paste- 
like  mass,  this  operation  being  carried  out  with  the  exclusion  of  air. 
It  is  also  stated  that  the  contact  material  may  be  reworked  in  the 
following  manner: 

It  is  first  purified  by  extraction,  the  nickel  removed  and  after  con- 
version of  the  latter  into  a  pulverulent  form  is  again  used  for  the 
production  of  nickel  carbonyl.  It  is  recommended  that  the  carbon 
monoxide  obtained  by  the  Linde-Caro  process  in  the  liquefaction  of 
water  gas  be  used  for  the  production  of  the  carbonyl. 

A  form  of  apparatus  adapted  to  be  used  in  carrying  out  a  process 
of  hydrogenating  oils  t  which  relates  more  specifically  to  the  treat- 
ment of  rancid  oils  or  oils  of  high  acidity  is  shown  in  Fig.  35.  An 
oil  containing  a  high  proportion  of  free  fatty  acids  or  products  of 
rancidification  may  be  diluted  with  a  neutral  oil  and  the  mixture 
hydrogenated  to  a  hard  fat,  although  the  original  rancid  oil  be  in- 
capable of  hydrogenation,  because  of  its  poisoning  action  on  catalyzers. 
The  apparatus  consists  of  a  tank  having  a  dome  in  which  atomizers 
are  mounted  and  by  which  the  oil  is  atomized  with  hydrogen  gas,  and 
is  then  allowed  to  trickle  through  a  series  of  screens  placed  in  the  lower 

*  Belgium  Patent  246,975. 

t  Zeit.  f.  angew.  Chem.  (1913),  ref.  627. 

t  Ellis,  U.  S.  Patent  1,078,136,  Nov.  11,  1913. 


44 


THE  HYDROGENATION  OF  OILS 


part  of  the  dome.  Palm  oil  may  be  heated  without  access  of  air  to  a 
temperature  at  which  its  color  is  destroyed  by  hydrogenating  under 
these  conditions,  producing  a  fat  which  is  especially  useful  to  soap 
makers. 

A  process  for  thickening  oilsand  fats  is  described  by  Scherieble.* 
The  material  to  be  treated  is  subjected  to  ozone-forming  electric 

discharges  by  sending  such  dis- 
charges directly  through  it. 
Potentials  of  10,000  to  20,000 
volts  yield  no  results,  as  oils  and 
fats  introduced  between  the  elec- 
trodes impede  any  discharge  by 
reason  of  their  great  insulating 
properties.  Experiments  in  this 
direction  have,  however,  shown 
that  discharges  through  oils  and 
fats  are  quite  possible  when  high 
potentials  of  .50,000  to  100,000 
volts  and  beyond  are  employed. 
The  higher  the  potential  of  the 
electric  current  and  the  greater 
its  frequency  the  easier  it  is  to 
pass  a  discharge,  with  the  for- 
FIG.  35.  mation  of  ozone,  through  thick 

layers  of  oil. 

The  oil  5  to  be  thickened  or  bleached  is  placed  in  the  pan  6  (Fig.  36), 
the  bottom  of  which  forms  one  electrode,  connected  to  the  source  of 
electricity  by  the  conductor  shown. 
The  second  electrode  8  having  the 
terminal  points  9  and  fed  through 
the  conductor  10  is  placed  above 
the  oil  so  that  the  discharge  11 
acts  upon  the  oily  material. 

By  the  Calvert  system  the  oil 
is  submitted  to  violent  agitation 
while  under  a  hydrogen  pressure 
of  250  pounds  per  square  inch  and 

at  a  temperature  of  180°  to  200°  C.,  in  a  specially  constructed  auto- 
clave having  an  electric  motor  (for  stirring)  enclosed  in  a  chamber 
which  is  under  the  same  hydrogen  pressure  as  the  autoclave  proper. 


FIG.  36. 


*  U.  S.  Patent  1,079,727,  Nov.  25,  1913. 


METHODS  OF  HYDROGENATION 


45 


The  motor  chamber  is  substantially  an  extension  of  the  autoclave, 
but  is  so  far  removed  from  the  latter  as  to  be  unaffected  by  the  heat. 

The  annexed  illustration,  Fig.  37,  represents  this  type  of  oil  hydro- 
genating  apparatus  which  the  Metropolitan  Laboratories  have  put 
on  the  market.  In  the  design  is  embodied  the  patented  principle  of 
enclosing  the  agitating  motor  in  a  chamber  essentially  an  extension  of 
the  autoclave  proper,  and  under 
the  same  gas  pressure.  By  this 
arrangement  the  risk  of  leakage 
is  entirely  eliminated,  and  at 
the  same  time  high  stirring 
speeds  are  rendered  possible 
without  the  frictional  resistance 
which  would  be  caused  by  shafts 
passing  through  glands,  etc. 
The  autoclave  proper  is  the 
lower  vessel  shown  in  the  illus- 
tration, and  is  enclosed  in  a 
heat-insulating  jacket.  The  top 
vessel  contains  the  electric 
motor,  the  intermediate  tube 
through  which  the  stirrer  shaft 
passes  being  enclosed  in  a  water 
jacket  in  the  larger  sizes.  Cur- 
rent is  conveyed  to  the  motor 
by  insulated  screws  on  the  top 
of  the  machine.  On  the  right 

is  the  flue  and  the   hydrogen  pIG  37 

feed    pipe,    the    charging    and 

discharging  tube  being  shown  on  the  left.  For  convenience  in  dis- 
charging the  contents,  in  the  smaller  sizes  the  whole  is  mounted  on 
trunnions. 

The  oil  is  brought  into  a  state  of  fine  division  by  the  stirrer  blades, 
which  cause  the  liquid  to  rotate  against  the  inner  side  of  the  vessel, 
to  which  perforated  baffle  plates  are  fitted.  The  working  pressure  is 
200  to  250  pounds  per  square  inch,  and  the  temperature  about  185°  C., 
but  every  machine  is  tested  to  1000  pounds  cold  water  and  to  500 
pounds  gas  at  200°  C.  The  illustration  represents  a  small  size,  suit- 
able for  oil  laboratories,  which  stands  about  4  feet  high,  but  large 
units  are  also  manufactured  for  working  in  batteries  on  a  commercial 
scale.* 

*  Chem.  Trade  Jour.  (1913),  618." 


46 


THE  HYDROGENATION  OF  OILS 


An  apparatus  for  hardening  oil,  proposed  by  Wilbuschewitsch,* 
comprises  the  vessel  R  (Fig.  38)  containing  the  fat  to  be  treated  and 
the  vessel  0  containing  the  catalyst.  Differentially-connected  pumps 
A  A'  feed  the  oil  and  the  catalyst  into  the  mixing  device  B  in  which  an 
intimate  mixture  of  the  oil  and  the  catalyst  is  obtained.  This  mixture 
passes  through  a  pipe  G  and  the  valve  H  into  an  autoclave  J'  which  is 
provided  with  a  spraying  device  C'  consisting  of  a  number  of  spraying 
nozzles  so  arranged  that  the  oil  and  catalyst  are  uniformly  scattered 


FIG.  38. 


in  finely-subdivided  condition  throughout  the  whole  inner  space  of 
the  autoclave.  A  compressor  K  forces  hydrogen  into  the  autoclave 
under  a  pressure  of  about  9  atmospheres.  The  pipe  X  extends  from 
the  upper  part  of  the  autoclave  downward  to  the  lower  end  of  the 
same  and  is  provided  at  its  lower  end  in  the  conical  lower  part  of  the 
autoclave  with  an  admission  nozzle  D'.  By  this  spraying  system  an 
intimate  contact  of  the  oil  mixture  with  the  hydrogen  is  achieved  on 
the  counter-current  principle.  The  autoclave  is  heated  to  between 
100°  to  160°  C.  according  to  the  nature  of  the  oil  under  treatment. 
The  reduction  by  the  hydrogen  begins  at  the  upper  part  of  the  auto- 
clave. The  partially  reduced  oil  mixture  collects  in  the  conical  part 
of  the  autoclave  and  is  sprayed  in  the  form  of  a  fountain  through  the 
autoclave  by  the  incoming  hydrogen.  The  mixture  is  forced  by  pump 
Ef  into  the  second  autoclave  J2.  The  hydrogen  enters  this  autoclave 
through  pipe  Y  and  the  action  of  the  first  autoclave  is  repeated.  Any 

*  U.  S.  Patent  1,079,278,  Nov.  18,  1913. 


METHODS  OF  HYDROGEN ATION  47 

number  of  such  autoclaves  can  be  arranged  in  series  or  parallel  to  each 
other  in  accordance  with  the  extent  of  reduction  required.  It  is 
generally  suitable  to  use  one  autoclave  for  each  increase  of  melting 
point  by  15°  C.  When  the  fat  has  attained  the  desired  melting  point 
which  is  ascertained  by  samples  withdrawn  from  the  autoclaves,  the 
oil  mixture  is  withdrawn  through  the  valve  U  into  the  centrifugal 
apparatus  F.  Here  the  oil  is  separated  from  the  catalyst.  The 
finished  reduced  oil  flows  into  the  reservoir  N  while  the  catalyst  is 
returned  through  the  pipe  Rf  and  valves  S  and  T  to  the  vessels  0  and 
P.  At  first  when  the  catalyst  which  Wilbuschewitsch  employs  is 
still  quite  fresh,  he  states  that  only  a  little  of  it  is  necessary  —  1  per 
cent  may  be  advantageously  used.  When,  however,  in  the  course  of 
the  operation  its  catalytic  power  decreases,  correspondingly  more  of 
it  must  be  used.  The  regulation  of  the  quantity  of  catalyst  may  be 
attained  by  a  suitable  adjustment  of  the  differential  pump  system. 
When  the  catalyst  is  completely  spent  it  is  allowed  to  flow  out  through 
the  valve  S  into  the  reservoir  P  in  order  to  be  regenerated.  The 
working  is  continued  by  introduction  of  fresh  catalyst  through  the 
valve  T.  The  hydrogen  not  consumed  passes  through  the  check 
valve  W  and  pipe  Q  and  cooling  worm  L  into  a  vessel  M  filled  with 
caustic  soda  lye  where  it  is  purified  and  then  passes  to  the  compressor 
and  autoclaves. 

Wimmer  and  Higgins  *  use  as  catalyzers  organic  metal  salts  such 
as  the  formates,  acetates  or  lactates  of  copper,  iron,  nickel  or  cobalt. 
These  require  no  special  preparation  before  their  use  as  catalytic 
agents;  and  it  is  claimed  that  impurities  contained  in  the  reducing 
gas  employed  in  the  treatment  do  not  render  these  compounds  in- 
effective. Wimmer  and  Higgins  state  that  those  processes  in  which 
finely-divided  metals  are  employed  in  the  treatment  of  unsaturated 
compounds  call  for  the  employment  of  intense  mechanical  agitation 
to  obtain  admixture  of  the  catalysts  and  the  liquid,  or  require  the 
distribution  of  the  metal  over  the  outer  surface  of  contact  carriers  such 
as  pumice  stone,  kieselguhr,  etc.  By  their  process  the  compound  to 
be  reduced  is  mixed  with  the  organic  metallic  salt,  heated  to  a  suitable 
temperature,  and  either  a  stream  of  the  reducing  gas  is  passed  through 
the  mixture,  or  the  latter  is  subjected  to  an  atmosphere  of  the  gas  in 
a  closed  vessel,  while  contact  between  the  gas  and  the  mixture  or 
emulsion  may  be  assisted  by  agitation.  Under  these  conditions  the 
saturation  is  said  to  take  place  comparatively  quickly  and  the  spent 
or  partly  spent  catalytic  agent  can  be  removed  by  simple  filtration 
after  the  operation. 

*  U.  S.  Patent  1,081,182,  Dec.  9,  1913. 


48 


THE  HYDROGENATION  OF  OILS 


According  to  an  example  given,  100  grams  of  cottonseed  oil  are  mixed  with  1  to 
5  grams  of  nickel  formate  (in  concentrated  aqueous  solution  or  in  the  form  of  a 
powder).  The  mixture  is  warmed  and  a  stream  of  hydrogen  gas  passed  into  the 
apparatus.  During  this  time  the  temperature  of  the  mass  is  raised  to  from  170°  to 
200°  C.  The  duration  of  the  treatment  depends  upon  the  quantity  of  the  catalytic 
agent  employed.  The  reduction  may  be  carried  out  until  the  unsaturated  compounds 
are  quantitatively  transformed  into  saturated  ones.  The  mass  is  then  filtered. 

For  this  process  they  regard  the  metal  salts,  both  normal  and  acid,  of  the  mono- 
and  polybasic  carboxylic  acids  and  hydrocarboxylic  acids  of  the  fatty  groups  as 
most  suitable;  the  formates,  acetates,  propionates,  butyrates,  lactates,  gly collates, 
oxalates,  malonates,  succinates,  tartrates  and  citrates  of  nickel,  cobalt,  iron  and 
copper  are  mentioned. 

"The  process  may  be  modified  in  various  ways.  Thus,  for  example,  the  oil  may 
be  emulsified  with  the  catalytic  agent  and  simultaneously  heated  and  have  hydro- 
gen or  gas  mixtures  containing  hydrogen  passed  through  it  in  a  suitable  emulsifying 
apparatus;  or  the  oil  mixed  with  the  catalytic  agent  may  be  brought  into  contact 
in  a  fine  state  of  division  with  the  hydrogen,  as  in  a  manner  that  has  already  been 
proposed.  The  reaction  may  also  be  accelerated  by  using  the  hydrogen  under 
pressure  or  by  impregnating  the  oil  with  hydrogen  and  then  bringing  it  into  intimate 
contact  with  the  catalytic  agent. " 


Fig.  39  is  a  view  of  an  apparatus  for  carrying  out  the  process.  The  gas  is  drawn 
by  a  pump  a  from  a  generator  (not  shown)  and  is  forced  by  the  pump  into  the  pres- 
sure equalizer  6.  Thence  the  gas  passes  through  a  pipe  c,  into  the  receptacle  e  pro- 
vided with  a  funnel  /  for  introducing  the  mixture  of  catalyzer  and  oil.  The  mixing 
apparatus  contains  an  agitator  consisting  of  a  longitudinal  shaft  provided  with  a 
series  of  revolving  beaters  g.  In  the  base  of  the  mixing  apparatus  is  mounted  a 
heater  h.  If  water  gas  is  used  as  the  reducing  agent,  the  portion  of  the  gas,  which 
has  not  been  absorbed  in  the  mixing  apparatus,  passes  through  a  pipe  i  to  a  gas  holder 
or  collector  k,  and  is  then  used  for  heating  or  power  purposes. 

A  modified  form  of  the  inductor  and  tank  shown  in  Fig.  26  is  de- 
picted in  Fig.  40.* 

In  Fig.  40,  1  is  a  treating  receptacle  having  the  inlet  2  for  oil  or  catalyzer;  a 
hydrogen  inlet  3;  a  back-flash  tube  4;  a  draw-off  valve  5;  a  steam  heating  coil  6; 
supporting  members  7;  and  a  catalyzer  inlet  8  adapted  to  hold  capsules  of  catalyzer; 

*  Ellis,  U.  S.  Patent  1,084,203,  Jan.  13,  1914. 


METHODS  OF  HYDROGENATION 


49 


11  is  a  pump  connected  with  the  lower  part  of  the  tank  by  the  pipe  12  and  having 
a  discharge  pipe  13  extending  to  an  inductor  14  which  is  in  communication  by  means 
of  the  inlet  15  and  pipe  16  with  the  top  of  the  treating  receptacle  1.  From  the 
inductor  the  pipe  17  extends  nearly  to  the  bottom  of  the  receptacle  and  terminates 
in  a  distributer  18  which  is  so  arranged  that  the  flow  of  material  therethrough  is 
both  down  and  angularly  against  the  bottom  of  the  tank  or  receptacle. 


FIG.  40. 

Bock*  describes  several  forms  of  apparatus  intended  for  hardening 
fats  and  fatty  acids.  '  One  of  these  involves  passing  the  fatty  material 
along  or  through  a  porous  plate  containing  catalyzer  in  the  presence  of 
hydrogen.  Fatty  acids  may  be  hardened  under  a  considerable  degree 
of  hydrogen  pressure  and  subsequently  the  catalyzer  may  be  freed  from 
the  acid  by  distillation  under  reduced  atmospheric  pressure.  Reduced 
nickel  on  kieselguhr  is  used  as  a  catalyzer.f 

*  Seifen.  Ztg.,  1914,  349. 

t  See  also  Seifen.  Ztg.,  1914,  421. 


CHAPTER  III 
METHODS  OF  HYDROGENATION— Continued 

IN  his  Inaugural  Dissertation,  Bedford  describes  a  series  of  obser- 
vations made  by  him  prior  to  or  during  1906  on  the  hydrogenation 
of  oleic  acid  and  certain  esters  of  the  fatty  acids  of  linseed  oil.* 

An  apparatus  as  shown  in  Fig.  40a  was  used  to  bring  oil,  hydrogen  and  catalyzer 
into  contact.  The  hydrogenating  portion  of  this  apparatus  consisted  of  two  com- 
municating vertical  cylinders  klk2  partly  filled  with  catalyzer  and  immersed  in  an 
oil  bath.  Oil  was  admitted  to  one  cylinder  by  means  of  a  dropping  funnel  while 
hydrogen  was  introduced  at  the  bottom  of  the  same  cylinder  through  the  glass  tube 
shown  on  the  right  hand.  The  catalyzer  was  prepared  by  igniting  nickel  carbonate 
to  form  the  oxide,  forming  the  latter  into  a  paste  by  means  of  distilled  (chlorine-free) 
water  and  adding  fragments  of  ignited  pumice  of  about  the  size  of  peas.  The 
pumice  and  nickel  oxide  paste  was  well  stirred,  the  material  dried  at  95°  and  reduced 
in  the  treating  apparatus  by  exposure  to  hydrogen  for  eight  hours  at  275°  to  285°  C. 
After  reduction  the  temperature  was  reduced  to  170°  to  180°  C.  and  the  oil  to  be 
hydrogenated  was  allowed  to  fall  drop  by  drop  on  the  nickelized  pumice  while 
hydrogen  was  passed  through  the  apparatus.  Under  these  conditions  hydro- 
genation took  place  and  the  treated  product  was  duly  separated  from  the  catalyzer 
by  extraction  with  ether.  The  nickelized  pumice  thus  freed  of  oil  was  used  again 
after  exposure  to  hydrogen  for  one  hour  at  a  temperature  of  250°  C. 

Bedford  determined  the  amount  of  hydrogen  absorbed  by  the  unsaturated 
compounds  examined  by  him  in  these  investigations  and  expressed  his  results 
in  part  in  terms  of  the  "hydrogen  number,"  that  is,  the  percentage  of  hydrogen 
absorbed  by  the  compound.  When  the  catalyzer  was  used  for  the  first  time 
abnormal  results  were  obtained,  due,  apparently,  to  the  incomplete  reduction 
of  the  nickel  oxide  in  the  preparation  of  the  catalyzer.  After  using  once,  more 
concordant  results  were  secured. 

Oleic  acid  having  an  iodine  number  of  87.5  was  treated  in  this  apparatus  and 
in  one  trial  the  reduction  product  had  an  iodine  number  of  4.1  and  a  melting- 
point  of  64.5°  C.,  while  in  another  case  the  iodine  number  was  0  and  the  melting- 
point  was  69°,  indicating  the  complete  transformation  of  oleic  to  stearic  acid. 

Pure  oleic  acid,  according  to  theory,  absorbs  0.714  per  cent  of  hydrogen.  This 
represents  the  hydrogen  number  of  oleic  acid.  In  two  trials  Bedford  found 

Hydrogen  Percentage  of 

Number  Theoretical 

Found.  .Amount. 

(A) 0.7226        101.2 

(£) 0.7450        104.3 

*  Uber  die  ungesattigten  Sauren  des  Leinols  und  ihre  quantitative  Reduktion  zu 
Stearinsaure,  Halle,  1906. 

50 


METHODS  OF  HYDROGENATION 


51 


When  the  ethyl  ester  of  linolenic  acid  was  similarly  treated  and  the  hydro- 
genated  product  (iodine  number,  0)  was  saponified,  stearic  acid  of  melting-point 
69°  C.  was  obtained. 

The  hydrogen  number  of  the  ethyl  ester  of  linolenic  acid  is  1.9737  and  the  results 
obtained  by  Bedford  were  as  follows: 


Hydrogen 
»    Number 
Found. 

(A) 1.9482 

(B) 2.0408 


Percentage  of 

Theoretical 

Amount. 

98.7 
103.4 


Bedford  also  hydrogenated  the  ethyl  esters  of  the  fatty  acids  of  linseed  oil 
(free  from  oleic  acid)  and  obtained  products  having  numbers  ranging  from  24.9 
to  0.  The  ethyl  ester  of  stearic  acid  was  the  main  product  of  the  reaction.  The 
hydrogen  number  of  the  ethyl  ester  of  linolenic  acid  is,  as  stated,  1.9737,  while 
that  of  linolic  acid  is  only  1.3072.  The  hydrogen  values  found  were  intermediate 
these  values. 


Hydi 


?en  Number 
found. 


(A) 1 .4544 

(B} 1 .4578 

(C) 1.4441 


FIG.  40a. 


The  complete  apparatus  used  by  Bedford  as  shown  in  Fig.  40 a  is  as  follows:  The 
glass  container  F  of  about  18  liters  capacity  is  used  for  holding  and  measuring  the 
hydrogen.  The  mouth  of  the  container  is  closed  with  a  stopper  having  two  perfora- 
tions through  which  the  tubes  rl  and  r2  are  inserted.  The  receptacle  is  surrounded 
with  a  metal  jacket  holding  water  which  enables  the  temperature  to  be  maintained  at 
the  desired  point.  From  the  container  F  the  tube  t  leads  to  an  intermediate  vessel 
E.  H  is  a  funnel  containing  water.  W  is  a  wash-bottle  containing  sulphuric 
acid.  Hydrogen  is  introduced  at  h2  and  nitrogen  at  h1.  S  is  a  glass  coil  cooled 
by  liquid  air  which  serves  for  the  removal  of  the  last  traces  of  moisture  from  the 
gases.  The  catalyzer  as  indicated  above  is  placed  in  the  vessels  A;1  and  A:2.  The 
vessel  B  is  cooled  with  liquid  air.  A  calcium  chloride  tube  b  is  placed  inter- 
mediate the  latter  and  the  tube  V.  Copper  oxide  is  introduced  into  the  tube 
V  and  in  this  tube  the  hydrogen  is  converted  into  water  and  the  latter  is  con- 
densed in  the  receptacle  A  by  chilling  with  liquid  air.  A  calcium  chloride  tube  is 
also  connected  with  the  exit  of  the  vessel  A. 

A  paper  by  Erdmann  and  Bedford  in  Berichte,  1909,  1324,  discusses 
the  hardening  of  fatty  acids  and  esters.  Reduced  nickel  on  pumice 


52  THE  HYDROGENATION  OF  OILS 

was  used  and  the  oil  was  allowed  to  flow  through  a  tower  containing 
the  catalyzer.  The  catalyzer  is  stated  to  be  based  on  a  modification 
of  the  method  of  Sabatier.  Linseed  oil  and  fatty  acids  were 
treated. 

The  continuous  hydrogenation  of  unsaturated  fatty  acids  or  esters 
may  be  carried  out  according  to  the  Badische  Co.*  in  the  following 
manner:  As  a  catalyzer  is  employed  nickel,  copper,  iron,  or  mixtures 
of  these  metals  with  one  another  or  with  agents  promoting  the  activity 
of  the  catalyzer.  The  process  is  effected  under  pressure  of  at  least 
thirty  atmospheres  and  preferably  over  fifty  atmospheres,  the  catalyst 
being  supported  in  the  pressure  vessel  so  as  not  to  mix  with  the  sub- 
stance treated.  The  preparation  of  the  catalyzer  may  be  accomplished 
by  reduction  of  an  oxygen  compound  of  the  metal  by  means  of  hydro- 
gen under  pressure  in  the  same  apparatus  used  for  the  hydrogenation 
of  the  fatty  acid,  etc.  According  to  examples:  finely  divided  nickel, 
prepared  by  reduction  of  the  oxide  or  carbonate  at  a  low  temperature, 
is  supported  on  a  carrier  in  the  pressure  vessel,  or  nickel  pieces  or  wire 
netting  is  suitably  held  therein.  Cottonseed  or  linseed  oil  is  passed 
into  the  vessel  and  treated  with  hydrogen  at  100°  under  a  pressure 
of  120  atmospheres.  Nickel  carbonate  or  formate  mixed  with  alumina 
and  formed  into  balls  or  spread  on  a  carrier,  is  placed  on  per- 
forated trays  in  a  cylindrical  high-pressure  apparatus  and  reduced  at 
220°  to  250°  by  means  of  hydrogen  under  pressures  of  30-100  atmos- 
pheres. The  reduced  metal  is  allowed  to  cool  in  hydrogen  under  a 
pressure  of  30-100  atmospheres.  The  reduced  metal  is  cooled  in 
hydrogen  to  about  80°,  and  a  stream  of  the  oil  to  be  hydrogenated 
and  hydrogen  under  pressure  are  theft  introduced  into  the  apparatus. 

A  laboratory  apparatus  for  catalytic  reduction  is  described  by 
Voswinckelf  which  in  a  modified  form,t  is  supplied  by  Bernhard 
To'macz  &  Co.,  Berlin.  Fig.  406  shows  the  hydrogen-measuring 
apparatus  employed. 

The  two  thick-walled  graduated  cylinders  G  and  Gi  are  drawn  out  at  their 
necks  in  order  to  do  away  with  the  rubber  stoppers  that  were  employed  in  the 
originally  designed  apparatus.  These  elongated  necks  are  bent  in  the  form  of 
an  L  and  are  connected  with  the  valves  A  and  A\  by  means  of  pressure  tubing. 
Of  the  rubber  tubes  b  and  61,  one  connects  the  apparatus  with  a  hydrogen  tank, 
while  the  other  joins  the  apparatus  to  a  reaction  vessel  of  the  shaking  type.  The 
entire  apparatus  is  mounted  on  a  wooden  frame  to  insure  stability  and  render  it 
easily  transportable. 

*  British  Patent  2,307,  Jan.  28,  1914;  Chem.  Abs.,  1916,  125;  J.  S.  C.  I.,  1915, 
970. 

tChem.  Ztg.,  1913,  489. 
%Ibid.,  1914,  634. 


METHODS  OF  HYDROGENATION 


53 


The  two  cylinders  which  are  joined  by  the  glass  tube  D  are  filled  with  1£  liters 
of  water.  By  means  of  air  or  hydrogen  the  water  is  transferred  into  the  cylinder 
Gi  until  the  latter  is  full.  The  valve  A\  is  then  closed  to  prevent  the  water  from 
flowing  back  in  G.  The  cylinder  G\  is  connected  with  the  hydrogen  tank  by 
means  of  61  and  the  water  is  displaced  by  hydrogen.  Valve  A  is  again  closed. 
The  hydrogen  tank  is  connected  with  6,  valve  A  is  opened  and  hydrogen  is  admitted 
until  the  pressure  is  about  1  §  atmospheres.  The  cylinder  G  is  then  connected  to 
the  reaction  chamber  whk-h  has  been  previously  eva  uated.  The  valve  Ai  is 
opened  and  the  shaking  machine  is  set  in  motion.  When  the  hyJrogen  of  the 
cylinder  G\  is  used  up,  the  cylinder  G,  which  in  the  meantime  has  been  filled  with 


FIG.  406. 

hydrogen,  is  connected  with  the  reaction  chamber  and  G\  is  connected  to  the 
tank  of  hydrogen.  During  this  operation  the  valves  A,  A\,  and  B  are  all  shut 
to  prevent  the  water  from  flowing  back  from  cylinder  Gi  into  cylinder  G. 

Fig.  40c  is  an  illustration  of  ja,  laboratory  type  of  hydrogenator.  On 
the  left  is  shown  an  autoclave  of  cast  steel  mounted  on  a  tripod  and 
equipped  with  a  stirrer.  The  latter  is  operated  by  a  grooved  pulley 
and  round  belt  which  is  supported  on  the  idler  shown  on  the  right. 
The  hydrogen  gas  is  supplied  by  the  pipe  shown  resting  on  the  base 
and  communicating  with  the  autoclave  through  the  top  of  the  latter. 
A  pressure  gauge  and  safety  valve  are  also  provided.  The  autoclave 
has  a  rounded  bottom  and  is  surrounded  by  a  sheet-iron  mantle.  It  is 
heated  by  a  Bunsen  burner.* 

*  The  autoclave  was  made  for  the  author  by  the  F.  J.  Stokes  Company,  Philadelphia,  Pa. 


54  THE  HYDROGENATION  OF  OILS 

Dewar  and  Liebmann  *  seek  to  produce  a  catalyst,  and  to  hydro- 
genate  oil  in  one  and  the  same  operation  and  at  the  same  relatively 
low  temperature  by  mixing  the  fats  or  oils  with  a  mixture  of  the  oxides 
(either  hydrated  or  anhydrous)  or  the  carbonates  of  two  or  more 
catalytic  metals,  viz.:  nickel,  cobalt,  or  copper,  or  with  a  mixture 
of  the  oxides  or  carbonates  of  one  or  more  of  these  catalytic  metals 
with  palladium,  platinum,  or  silver,  in  a  fine  state  of  division,  or 
with  a  mixture  of  the  oxides  or  carbonates  of  one  or  more  of  these 


FIG.  40c. 

catalytic  metals  with  silver  oxide,  passing  hydrogen  through  the 
mixture  while  it  is  being  stirred  and  heating  the  mixture  to  a  tem- 
perature at  which  the  reduction  takes  place.  Hydrogenation  pro- 
ceeds concurrently  with  the  production  of  the  catalyst  and  the  con- 
version of  the  unsaturated  body  by  the  addition  of  hydrogen  to  the 
molecule  is  said  to  be  very  rapid. 

The  modifications  of  the  process  are  classified  by  Dewar  and  Liebrrann  as 
follows : 

A.  Hydrogenation  of  fats  and  oils  in  a  liquid  state  by  treatment  with  hydrogen 
of  an  unsaturated  fat  or  oil  in  the  presence  of  mixtures  of  hydroxides,  oxides,  or 
carbonates  of  two  or  more  of  the  catalytic  metals,  viz.,  nickel,  cobalt,  or  copper. 

*J.  S.C.I.,  1915,  797;  British  Patent  12,982  of  1913;  Mat.  grasses  1915,  8,  4377; 
Chem.  Abs.,  1916,  284. 


METHODS  OF  HYDROGENATION  55 

B.  Hydrogenation  of  fats  and  oils  in  a  liquid  state  by  treatment  with  hydrogen 
of  an  unsaturated  fat  or  oil  in  the  presence  of  a  mixture  of  one  or  more  of  the 
metallic  compounds  as  denned  in  A  with  finely-divided  palladium,  platinum,  or 
silver. 

C.  Hydrogenation  of  fats  and  oils  in  a  liquid  state  by  treatment  with  hydrogen 
of  an  unsaturated  fat  or  oil  in  the  presence  of  a  mixture  of  a  metallic  compound 
as  defined  in  A  and  silver  oxide. 

D.  Hydrogenation  of  fats  and  oils  in  a  liquid  state  by  treatment  with  hydrogen 
of  an  un=aturated  fat  or  oil  in  the  presence  of  the  mixtures  mentioned  in  A,  B 
and  C,  produced  on  the  surfaces  of  porous  substances. 

The  following  examples  will  serve  to  illustrate  the  process: 

1.  A  solution  of  89.2  parts  by  weight  of  nickel  nitrate  (crystals)  and  of  9.3 
parts  of  copper  nitrate  (crystals)  is  poured  into  a  hot  sol  jtion  containing  46  parts  of 
potassium  carbonate.     The  precipitate  is  collected  on  a  filter,  washed  thoroughly 
until  free  from  soluble  salts  and  then  dried  on  the  water-bath;    it  is  then  heated 
to  a  temperature  below  red  heat  until  the  weight  is  constant.     One  hundred  parts 
of  cottonssseJ  oil  are  then  stirred  with  a  quantity  of  the  oxide  thus  prepared, 
the  metal  contents  of  which  correspond  to  two  per  cent  of  the  weight  of  the  oil. 
A  strong  current  of  hydrogen  is  passed  through  the  mixture  which  is  heated  for 
two    hours  at  about  190°  C.  while  being  continuously  stirred.     On  cooling,  the 
oil  is  found  to  be  hard  and  very  nearly  saturated,  the  iodine  number  being  reduced 
from  110.6  of  the  original  oil  to  20.4. 

A  similar  experiment  carried  out  with  the  same  mixture  of  oxides  and  whale 
oil  shows  after  an  hour  reduction  of  the  iodine  value  from  114.8  to  20.6  and  after 
two  hours  to  1.9. 

2.  One  hundred  parts  of  whale  oil  are  mixed  with  a  quantity  of  nickel  and 
copper  hydrates  (containing  90  per  cent  of  metallic  nickel  and  10  per  cent  of 
copper)  in  proportion  of  about  2  per  cent  of  the  metals  to  the  weight  of  the  oil 
and  a  strong  current  of  hydrogen  is  passed  through  the  mixture  while  it  is  being 
continuously  stirred  and  heated  for  one  hour  at  about  185°  C.     The  iodine  value 
of  the  whale  oil  is  thus  reduced  from  128.8  to  32.3  and  the  oil  is  quite  hard. 

3.  Nickel  and  copper  carbonates  are  prepared  in  molecular  proportions  in  the 
manner  described  in  No.  1,  and  a  quantity  of  the  carbonate,  the  metal  contents 
of  which  amount  to  about  2  per  cent  of  the  weight  of  the  oil  used,  is  mixed  with 
cottonseed  oil  and  a  strong  current  of  hydrogen  is  passed  through  the  mixture, 
while  it  is  being  continuously  stirred  and  heated  for  two  hours  to  about  185°. 
The  iodine  value  is  reduced  from  113  to  38.6. 

4.  44.6  parts  of  nickel  nitrate  (crystals)  and  2  parts  of  palladium  chloride  are 
dissolved  in  water  with  the  addition  of  a  little  hydrochloric  acid.     The  solution 
is  warmed  and  added  to  a  hot  aqueous  solution  containing  15  parts  of  caustic  soda 
and  2  parts  by  volume  of  40  per  cent  formalin.     A  dark  gray  precipitate  is  obtained, 
collected  on  a  filter  and  dried  on  the  water-bath. 

One  hundred  parts  of  whale  oil  are  mixed  in  an  autoclave  with  3  parts  of  the 
product  thus  prepared  (about  2  per  cent  of  metal  contents)  the  autoclave  closed 
and  the  mixture  being  well  stirred  and  heated  (while  hydrogen  is  passed  through) 
to  about  180°  or  190°,  the  outlet  of  the  hydrogen  being  so  regulated  that  the 
pressure  in  the  autoclave  is  about  140  Ib.  After  half  an  hour  the  oil,  on  cooling, 
is  quite  hard,  the  iodine  number  being  reduced  from  128.8  to  36.1. 

5.  Whale  oil  is  mixed  with  nickel  hydrate  and  silver  oxide  (90  per  cent  nickel 
and  10  per  cent  silver)  in  proportion  of  about  2  per  cent  of  the  combined  metals 


56  THE  HYDROGENATION   OF  OILS 

to  the  weight  of  the  oil  used.  A  strong  current  of  the  hydrogen  is  passed  through 
the  mixture  for  two  hours  while  it  is  being  continuously  stirred  and  heated  up  to 
c.bout  195°.  The  iodine  value  of  the  oil  is  reduced  from  114.8  to  62.1. 

6.  Asbestos  is  impregnated  with  a  solution  containing  equal  parts  of  nickel 
nitrate  (crystals)  and  copper  nitrate  (crystals)  in  such  strength  that  the  metal 
contents  of  asbestos  and  oxides,  after  their  product  on,  amount  to  20  per  cent 
of  the  combined  weight  of  metal  and  carrier.  The  impregnated  asbestos  is  dried 
and  heated  to  convert  the  nitrates  into  oxides.  Seventy-five  parts  of  cotton- 
seed oil  are  mixed  in  an  autoclave  with  5.5  parts  of  the  asbestos  thus  prepared 
(the  metal  contents  amounting  to  about  1  per  cent  of  the  oil)  the  auto:  lave  is  closed 
and  the  mixture  heated  while  being  well  stirred  and  hydrogen  is  passed  through 
it  at  about  180°  to  190°.  The  outlet  of  the  hydrogen  is  so  regulated  that  the  pres- 
sure in  the  autoclave  is  about  140  Ib.  After  half  an  hour  the  oil  on  cooling  is 
quite  hard  and  practically  converted  into  a  saturated  compound,  the  iodine  value 
being  reduced  from  113  to  2.7.* 

Dewar  and  Liebmann  treat  fats  and  oils  with  hydrogenf  in  the 
presence  of  a  catalyst  distributed  over  a  mass  of  fibrous  and  coherent 
material  or  yarns  or  fabrics  made  therefrom,  and  arranged  so  that 
fibers  will  not  become  separated  from  one  another.  With  this  arrange- 
ment the  tedious  operation  of  nitration  is  avoided. 

The  fibrous  material  may  consist  of  cotton,  hemp,  flax,  or  jute,  wool,  silk,  or 
similar  natural  organic  fibrous  materials,  or  even  artificial  silk,  e.  g.,  viscose  silk 
freed  from  sulphur.  Sponge  also  may  be  used.  Separation  of  the  fibers  is  pre- 
vented by  enclosing  the  masses  between  screens  of  gauze  or  other  suitable  material, 
or  by  securing  with  wires  or  threads;  or  if  yarns  or  fabrics  are  used,  these  may 
be  wound  round  or  otherwise  secured  to  the  blades  of  an  agitator  or  to  fixed 
supports.  If  strongly  adherent  masses  of  fibrous  materials,  such  as  cotton,  silk 
or  flax,  or  yarns  or  fabrics  made  therefrom,  be  used,  the  masses  may  be  left  free 
to  move  in  the  liquid,  but  the  products  of  hydrogenation  are  not  so  satisfactory. 
If  nickel,  cobalt,  or  copper  is  used  as  the  catalyst,  the  oxide  or  carbonate  of  the 
metal  is  distributed  on  the  support,  and  the  catalyst  produced  before  or  during 
the  process  of  hydrogenation.  In  the  case  of  the  platinum  group  of  metals,  the 
catalyst  is  prepared  by  impregnating  the  materials  with  a  platinum  or  like  salt 
solution  and  then  treating  with  a  hot  alkaline  solution  of  formaldehyde.  In 
examples,  cotton  or  linen  yarn,  or  bleached  artificial  silk  yarn  freed  from  sulphur 
or  asbestos  cord  is  passed  through  a  solution  of  nickel  and  copper  compound,  and 
after  squeezing,  treated  with  soda  solution  and  dried.  The  material  is  wound 
on  a  nickel  gauze  cylinder  or  on  the  blades  of  the  agitator,  and  placed  in  an  auto- 
clave with  the  oil.  In  another  example,  silk  yarn,  on  which  nickel  and  copper 
carbonates  were  distributed  as  in  the  previous  example,  is  wound  on  the  plates 
of  an  agitator  and  washed,  first  with  water  and  then  with  rickel  acetate  solu- 
tion and  finally  with  water.  | 

*  See  Canadian  Patent,  Procter  &  Gamble  Co.,  178,021,  July  3/1917;  Chem.  Abs. 
12,  98. 

t  British  Patent  15,668,  June  30,  1914;  J.  S.  C.  I.,  1915,  1102;  Chem.  Abs.  1916, 
125. 

t  U.  S.  Patent,  1,222,608,  Aug.  17,  1917-  Canadian  Patent,  Procter  &  Gamble 
Co.,  178-,020,  July  3,  1917, 


METHODS  OF  HYDROGENATION 


57 


A  process  of,  and  apparatus  for,  making  lard  substitute  is  proposed 
by  Chisholm.* 

In  Fig.  4(W,  a  casing,  mounted  upon  supports,  is  provided  at  the  top  with 
a  pressure  gauge  and  a  gas  outlet  which  may  be  set  to  discharge  the  gas  at 
any  desired  pressure.  Centrally  and  rotatably  mounted  within  the  chamber  is 
a  catalyzing  element,  consisting  of  a  spool-like  support  wound  with  wire  formed 
of  or  coated  with  a  catalytic  agent,  the  wound  mass  being  sufficiently  porous 


Hydrogen 
Inlet 


FIG.  4(R 

to  permit  of  the  passage  of  liquid  and  gas  outwardly  therethrough,  the  liquid 
and  gas  tending  to  follow  the  spiral  course  of  the  wire  in  its  passage  outward. 
In  the  construction  of  the  catalyzing  element,  No.  20  copper  wire  with  a  rough 
black,  unpolished  electrolytic  deposit  of  nickel  thereon  is  used.  Wire  of  nickel 
or  palladium  which  has  been  roughened  also  may  be  employed.  Within  the 
spirally  wound  mass  of  wire  is  a  central  chamber  with  which  there  is  rigidly 
connected  an  inlet  pipe  to  provide  hydrogen  gas.  A  pipe  on  the  opposite  side 

*U.  S.  Patents  Nos.  1,113,151,  Oct.  6,  1914;   1,114,963,  Oct.  27,  1914;  J.  S.  C.  I.,  1914, 
1062,  1168;  Chem.  Abs.,  1914,  3828;  1915,  110. 


58  THE  HYDROGENATION  OF  OILS 

supplies  oil  to  the  apparatus.  The  pipes  are  rotatably  mounted  within  bearings 
secured  upon  opposite  sides  of  the  casing  and  the  oil  pipe  is  provided  with  a 
driving  pulley.  A  satisfactory  size  for  the  casing  is  3  ft.  6  in.  in  diameter  and 
6  in.  thick  with  inlets  at  opposite  sides  of  |  in.  The  catalytic  agent  may  have 
a  diameter  of  23  in.  and  a  thickness  of  5|  in.,  the  inner  chamber  being  approx- 
imately 3  in.  in  diameter.  On  being  revolved,  the  catalyzing  element  moves 
the  oil  and  gas  outwardly  along  the  lines  of  the  spirally-wound  wire.  A  tem- 
perature of  160°  is  employed.  The  hydrogen  and  oil  may  be  introduced  under 
pressure.  The  lard-like  fat  resulting  from  the  treatment  of  cottonseed  oil  in 
this  manner  is  collected  in  the  lower  part  of  the  casing. 

Kimura  *  agitates  an  unsaturated  fatty  oil,  a  catalyst  such  as 
nickel  carbonate  and  hydrogen  gas  in  a  vertical  cylinder  enclosed  in 
a  steam  jacket. 

A  central  vertical  shaft  carries  an  agitator  comprising  a  framework,  star-shaped 
in  horizontal  cross-section,  each  radial  portion  being  covered  by  metallic  netting  of 
nickel,  platinum,  iron,  or  silver.  The  central  shaft  also  carries  a  supporting  spider 
for  the  spindles  of  similar  planet  agitators  which  thus  revolve  around  the  central 
agitator.  Each  planet  spindle  carries  a  spur-wheel  which  engages  with  an  internally 
toothed  ring  on  the  wall  of  the  container.  The  central  agitator  causes  a  centrifugal 
movement  of  the  liquid  outwards,  and  the  rotation  of  the  planet  agitators  causes 
an  intimate  mixing  and  subdivision. 

An  endeavor  has  been  made  by  Rather  and  Reid  f  to  determine  the 
nature  of  the  reaction  between  ethylene  and  hydrogen  from  the 
quantitative  standpoint.  The  method  employed  for  bringing  about 
reaction  differs  from  that  of  Sabatier  and  Senderens  of  passing  a 
mixture  of  gas  or  vapor  and  hydrogen  over  reduced  nickel  in  a  long 
tube.  The  method  of  Rather  and  Reid  to  a  certain  extent  is  a  sort 
of  combination  of  the  Sabatier  and  Senderens  method  and  the  present 
method  of  hydrogenating  non-volatile  oils  by  agitating  with  a  catalyst 
while  bringing  hydrogen  into  contact  with  the  oil. 

Details  of  the  experimental  work  carried  out  by  Rather  and  Reid  are  given 
below : 

Preparation  of  the  Catalyst.  One  hundred  grams  of  infusorial  earth  were  treated 
with  a  solution  of  50  g.  nickel  nitrate,  Ni(NO3)2-6H2O,  in  about  150  cc.  water, 
and  the  resulting  moist  mass  added  to  a  strong  water  solution  of  60  g.  sodium 
carbonate,  Na2CO3  •  10H2O,  to  precipitate  the  nickel  as  carbonate.  The  product 
was  well  washed  and  dried  and  the  nickel  carbonate  reduced  by  heating,  in  a  glass 
tube,  just  below  red  heat,  in  a  current  of  pure  dry  hydrogen  till  no  more  water 
was  formed,  and  cooled  in  a  current  of  pure  dry  carbon  dioxide.  In  order  to 
standardize  the  catalyst,  its  activity  was  tried  with  cottonseed  oil,  70  g.  of  th* 
oil  and  1  g.  of  the  catalyst  being  treated  with  pure  dry  hydrogen  at  180°  in  the 
apparatus  described  on  p.  76.  The  iodine  number  of  the  oil  was  lowered,  in 

*  British  Pat.  113,232,  Aug.  31,  1917;  J.  S.  C.  I.,  1918,  187. 
t  J.  Am.   Chem.   Soc.,  1915,   2115, 


METHODS  OF  HYDROGENATION  59 

sixty  minutes'  treatment,  from  113.7  to  44.6.  Experiment  showed  that  the  cat- 
alyst did  not  deteriorate  appreciably  during  the  time  that  each  portion  of  it  was 
in  use. 

Temperature.  In  all  of  the  experiments,  the  temperature  was  maintained 
at  180°±1°  by  immersing  the  bulb  of  the  reaction-flask  in  an  oil-bath,  the  tem- 
perature of  which  was  maintained  constant  by  an  oil  thermostat  with  mercury 
contacts,  controlling  a  gas  regulator. 

Materials.  The  ethylene  was  made  according  to  method  of  Senderens  and 
washed  with  codium  hydroxide  solution.  The  hydrogen  was  from  zinc  and  acid 
and  was  washed  with  alkaline  potassium  permanganate.  As  an  inert  medium,  in 
which  to  suspend  the  catalyst,  melted  parafiine  was  used. 

Procedure.  The  gas  mixtures  were  prepared  in  gasometers,  holding  about 
24  1.,  which  were  provided  with  an  arrangement  for  maintaining  nearly  constant 
pressure.  The  same  lot  of  the  mixture  was  used  fo  the  whole  series  of  experi- 
ments on  any  one  proportion.  Each  mixture  was  analyzed  for  ethylene  by  the 
usual  method  with  fuming  sulphuric  acid.  Ihe  mixture  o  gases  was  run  through 
concentrated  sulphuric  acid  to  dry  it  and  then  into  the  reaction  flask  which  con- 
tained, in  each  experiment,  1  g.  of  the  catalyst,  and  70  g.  of  the  paraffine.  The 
stirrer  was  run  at  3300  to  3500  r.p.m.  In  each  case,  time  was  allowed  for  the  dis- 
placement of  air  from  the  apparatus  and  for  the  hot  paraffine  to  come  to  equi- 
librium with  the  ethylene  hydrogen,  and  ethane  passing  through  it.  The  attain- 
ment of  this  equilibrium  was  shown  by  constancy  in  the  analysis  of  the  successive 
samples  of  the  issuing  gases.  The  amount  of  ethane  in  the  product,  which  is  the 
same  as  the  percentage  of  reduction  of  the  ethylene,  was  calculated  by  the  following 
formula,  in  which  E\  is  the  percentage  of  ethylene  in  the  original  mixture  and 
EZ  is  the  percentage  of  ethylene  in  the  products  of  the  reaction. 

100^-100^2 

Ethane  =  —  — . 

100  -E, 

Fresh  lots  of  catalyst  and  paraffine  were  used  for  each  24  1.  of  mixture.  The  rate 
of  gas  flow  and  the  composition  of  the  original  mixture  are  the  only  variables 
studied. 

The  results  are  by  no  means  as  regular  as  could  be  wished,  and  some  are 
evidently  out  of  relation  to  the  others.  They  are  not  to  be  considered  as  final. 
The  irregularities  may  depend  on  factors  not  as  yet  known  or  controlled.  In 
Fig.  40e  the  percentage  of  the  ethylene  reduced  is  plotted  against  the  rate  of  flow. 
The  interesting  result  is  that,  for  all  of  the  mixtures,  about  70  per  cent  of  the 
ethylene  is  reduced  when  the  rate  of  flow  is  10  cc.  per  minute.  All  of  the  results 
for  the  10  per  cent  mixture  are  regular  and  as  would  be  expected.  Those  for 
mixtures  containing  higher  percentages  of  ethylene  are  by  no  means  so  regular 
and  the  curves  are  in  unexpected  relations  to  each  other.  Doubtless  the  deter- 
mining factor  is  solubility.  The  reaction  is  probably  taking  place  between  the 
ethylene  and  the  hydrogen  that  are  dissolved  in  the  paraffine.  The  mass  law  then 
holds  for  this  solution  and  not  for  the  gases  that  are  not  in  solution.  When  the 
passage  of  the  gas  mixture  is  rapid,  the  gases  are  swept  through  before  equilibrium 
can  be  established  between  the  gas  mixture  and  the  solution. 

In  Fig.  40/  the  volume,  in  cc.,  of  gases  made  to  combine,  per  minute,  is  plotted 
against  the  rate  of  flow.  As  was  to  be  expected,  this  amount  increases  with  the 
amount  of  the  gas  mixture  that  is  exposed  to  the  action  of  the  catalyst.  The  results 


60 


THE  HYDROGENATION  OF  OILS 


for  the  different  mixtures  are  in  the  expected  order,  those  for  the  rate  of  100  cc. 
per  minute  being  the  most  instructive.  Under  these  circumstances,  in  the  50 
per  cent  mixture,  17  cc.  of  hydrogen  is  made  to  combine  with  17  cc.  of  ethylene 
in  one  minute.  Since  the  1  g.  of  the  catalyst,  as  prepared,  cannot  contain  more 
than  0.1  g.  nickel,  the  volume  of  this,  considered  as  Ni,  would  be  about  0.01  cc. 
or  less.  Hence  the  catalyst  induces  the  reaction  in  3400  times  its  own  volume  of 
the  gas  mixture  in  one  minute.  In  the  experiment  with  cottonseed  oil,  given  above, 
the  same  amount  of  nickel  caused  the  absorption  of  4230  cc.  of  hydrogen  or  423,000 
times  its  own  volume  of  hydrogen  in  sixty  minutes,  or  7000  times  its  own  volume 
in  each  minute.  These  volumes  are  calculated  for  a  temperature  of  0°  and  would 
be  67  per  cent  greater  at  180°,  at  which  the  action  really  took  place.  The  amount 
of  hydrogen  caused  to  combine  with  the  oil  is  several  times  as  great  as  the  amount 


10%  - 

20%  .......... 

32%  ----- 

JO  %......_ 


10  25  JO         JOO  200 

Rate  ^  Gas  Flow  in  cc- per  minute 

FIG.  40e. 


10  25  30  I 00  200 

"Rate  of  Gas  How  tncc-perm/nute 

FIG.  40/. 


combined  with  the  ethylene,  which  is  as  would  be  anticipated,  as  the  concentra- 
tion of  the  ethylene  in  the  paraffine  is  probably  much  smaller  than  the  concentra- 
tion of  the  oleine  in  the  oil,  and  the  partial  pressure  of  the  hydrogen  in  the  mix- 
ture is  only  half  so  great  as  in  the  pure  hydrogen.  However,  the  results  are  of 
the  same  order  of  magnitude. 

In  the  process  of  Asp  Bock  (see  p.  49)  of  treating  fats  with  hydrogen 
a  porous  metal  in  the  form  of  plates  or  blocks,  is  used  as  a  catalyzer. 
Either  the  hydrogen  and  fatty  acids  are  allowed  to  pass  in  vapor 
form  through  the  porous  metal,  or  the  oil  is  passed  through  the  porous 
metal  at  the  ordinary  temperature  and  pressure  while  the  hydrogen 
rises  through  the  pores.  These  methods  may  be  combined.  The 
first  method  is  preferred  for  fatty  acids,  the  other  for  glycerides.  * 

A  hydrogenation  process  employing  hydrogen  under  pressure  is 
proposed  by  David, f  according  to  which  gas  is  forced  into  the  lower 

*Chem.  Abs.,  1915,  868;    Danish  Patent  18,332,  March  27,  1913. 
t  J.  S.  C.  I.,  1915,  186;    French  Patent  470,392,  June  14,  1913. 


METHODS  OF  HYDROGENATION 


61 


a 


part  of  the  first  of  a  series  of  connected  cylinders  containing  the 
mixture  of  melted  fat  and  catalytic  agent.  The  fat  is  intermittently 
projected  upwards  and  falls  from  depending  plates,  preferably  of 
nickel,  into  the  current  of  gas,  while  a  hot-air  jacket  maintains  the 
temperature  at  150°  to  200°  C.  The  hydrogen  passes  through  several 
of  the  cylinders  before  being  returned  to  the  gas  holder  to  be  purified, 
compressed,  and  used  again. 

Adam  *  secures  intimate  contact  between  the  reacting  materials 
in  the  catalytic  hydrogenation  of  liquids,  by  bubbling  the  gas  from 
a  number  of  points  into  a  body  of  liquid,  coalescence  of  gas  bubbles 
from  adjacent  delivery  points  being  prevented  by  suitable  partitions. 

A  form  of  Adam's  apparatus  is  shown  in  Fig.  400. 

In  this  apparatus  a  tall  vessel  a  is  provided  with  an  assemblage  of  tubes 
b,  supported  by  the  supports  c.  These  tubes  are  set  closely  together  and  are 
open  at  both  ends.  They  may  be  of  any  desired 
cross-sectional  form,  and  although  shown  straight 
may  be  somewhat  spiralled  where  increased  con- 
tact is  desired.  Beneath  the  tubes  and  at  a  little 
distance  away  is  a  gas  manifold  d  connected  to  the 
gas  supply  duct  e  leading  from  the  upper  part  of 
the  vessel  /,  to  the  blower  h.  From  the  gas  mani- 
fold nozzles  k  project  in  to  the  tubes  6.  Gas  is 
introduced  at  g. 

By  appropriate  choice  of  the  relative  diameter 
and  height  of  the  tubes,  the  number  of  nozzles 
to  each  tube,  and  adjustment  of  the  gas  flow,  and 
of  the  height  of  the  liquid  supplied  to  the  tubes 
the  character  of  the  contact  can  be  varied  from 
that  of  a  climbing  film  to  that  of  a  tall  column  of 
froth. 

The  heating  of  the  material  can  conveniently  be 
effected  by  electric  heaters  immersed  therein,  and 
these  may  be  formed,  for  instance,  by  insulating  the 

tubes  from  each  other  at  the  top  and  bottom,  and  so  converting  them  into  a 
series  of  heating  elements. 

In  the  Griiner  process  of  bleaching  and  thickening  oils  and  fats  f  electric 
currents  are  passed  through  the  material  in  an  acid  atmosphere,  the  tension 
and  frequency  of  the  discharges  being  such  that  the  mass  is  kept  in  vigorous 
motion. 

Roentgen  rays  have  been  suggested  as  an  aid  in  hydrogenating 
fats.  Wielgolaski  %  brings  hydrogen  into  contact  in  various  ways 
with  fats  or  fatty  acids  while  exposing  the  material  to  Roentgen  rays. 

*J.  S.  C.  I.,  1914,  1226;    British  Patent  24,815,  Oct.  31,  1913. 
t  Holland  Patent  1,142,  Feb.  4,   1916;    Chem.  Abs.,   1916,   1715. 
$  Seifen  Ztg.,  1914,  1195;    Norwegian  Patent  24,528,  1913. 


FIG.  400. 


62  THE  HYDROGENATION  OF  OILS 

In  one  case  *  oils  are  passed  through  electrodes  which  have  a  porous 
filter-like  form  and  are  subjected  to  electrical  action,  f 

Experiments  were  performed  by  Custis  t  to  ascertain  if  there  would 
be  an  acceleration  of  the  hydrogenation  of  oleic  acid  under  the  influence 
of  the  rays  from  an  iron  arc.  The  hydrogen  was  led  into  a  quartz 
flask,  which  contained  the  oleic  acid.  A  long  air  condenser  was  passed 
through  the  stopper  with  which  the  flask  was  supplied.  An  iron 
arc  was  placed  1.5  centimetres  from  the  flask,  and  exposure  was  allowed 
to  proceed  for  six  hours.  From  the  iodine  numbers  of  the  acid  before 
and  after  treatment  the  conclusion  was  reached  that  there  is  no 
acceleration  in  the  hydrogenation  of  oleic  acid  when  hydrogen  acts  on 
the  acid  in  the  presence  of  rays  from  an  iron  arc  under  ordinary 
conditions  of  temperature  and  pressure.  Blank  experiments  showed  an 
amount  of  saturation  equivalent  to  that  found  in  the  exposed  fatty  acid. 

Charlton,§  has  devised  apparatus  by  which  saturation  is  effected 
in  a  closed  rotating  drum  provided  on  its  inner  periphery  with  blades 
which  break  up  the  oil  and  bring  it  into  intimate  contact  with  hydro- 
gen. The  gas  is  introduced  under  pressure  through  a  flexible  tube 
and  a  reducing  valve  from  a  cylinder  attached  to  the  drum  and  moving 
with  it.  Steam  is  admitted  to  an  outer  casing  of  the  drum  through 
a  passage  in  one  of  the  trunnions  and  escapes  through  the  other  trun- 
nion. The  drum  is  preferably  made  to  rotate  nearly  a  complete 
revolution  alternately  in  opposite  directions. 

An  apparatus  is  described  by  Verona  Rinati  ||  for  the  hydrogenation 
of  oils,  in  which  palladium  precipitated  on  small  pieces  of  coke  is  used 
as  a  catalyst. 

The  catalytic  material  is  placed  on  a  movable  support  kept  in  motion  by  a 
rotating  spindle  connected  by  gearing  with  a  pulley  outside  the  reaction  chamber. 
Oil  which  has  previously  been  heated  is  sprayed  into  the  upper  part  of  the 
chamber  by  means  of  hydrogen  under  pressure,  and  a  pressure  of  about  two 
atmospheres  is  maintained  inside  the  chamber.  Three  reaction  chambers  are 
provided  and  the  oil  may  be  withdrawn  after  one,  two,  or  three  treatments, 
according  to  the  degree  of  hydrogenation  desired.  The  hydrogen  is  obtained 
from  water-gas  by  the  Frank-Linde-Caro  process  of  refrigeration,  and  all  the 
excess  coming  from  the  reaction  chambers  is  returned  to  the  refrigerating  appa- 
ratus for  purification.  When  the  catalyst  loses  its  activity,  it  is  washed  in  the 
apparatus  with  an  inert  solvent  (benzine),  the  last  traces  of  the  latter  are 
expelled  by  a  current  of  steam,  and  the  palladium  is  again  rendered  active  by 

*  Norwegian  Patent  No.  25,009. 

t  A  full  description  is  given  in  Seifen  Ztg.,  1915,  73. 
t  J.  Frank.  Inst.,  1917,  880. 

§J.  S.  C.  I.,  1915,  289;    British  Patent  1,410,  Jan.  19,  1914. 

||  Annali  Chim.  Appl.,  1914,  2,  99-105;  J.  S.  C.  I.,  1914,  1061;  Chem.  Aba., 
1914.  3723. 


METHODS  OF  HYDROGENATION 


63 


treatment  with  hydrogen  at  not  above  150°  C.  Palladium  possesses  the  advan- 
tage of  being  active  at  a  considerably  lower  temperature  than  nickel  (e.g.,  at 
80°  to  90°  C.). 

At  the  Vereinigte  Chem.  Werke  at  Charlottenberg,  according  to 
Colletas  *  hydrogenation  of  oils  is  effected  at  100°  C.,  under  a  pressure 
of  2  to  3  atmospheres  by  means  of  0.00002  part  of  palladium  chloride 
in  the  presence  of  an  alkali.  The  loss  of  catalytic  agent  is  from  5  to 
7  per  cent  of  the  weight  taken,  which  corresponds  to  an  expense  of 
1.60  francs  per  100  kilos  of  fat. 

A  simple  and  effective  method  of  treating  oils  containing  finely- 
divided  catalyzer  with  hydrogen  is  described  by  the  author  f  accord- 


FIG.  40ft. 


FIG.  40i. 


ing  to  which  the  oil  and  catalyzer  is  exposed  to  an  ascending  current 
of  the  gas.  The  oil  and  catalyzer  mixture  is  caused  to  circulate  in 
a  direction  approximately  transverse  to  the  direction  of  flow  of  the 
stream  of  hydrogen. 

Apparatus  for  the  purpose  is  shown  in  Fig.  40A.  A  treating  tank  is  equipped 
with  a  shaft,  carrying  mixing  blades.  Hydrogen  is  entered  by  a  pipe  at  the 
bottom  and  passes  out  of  the  apparatus  by  an  exit  pipe  at  the  top.  The  bell- 
shaped  affairs  on  the  shaft  may  be  used  for  the  purpose  of  intercepting  the 
upward  flow  of  the  gas,  permitting  of  a  longer  period  of  contact.  The  tank  is 
filled  with  oil  containing  catalyzer,  finely-divided  nickel  from  nickel  carbonyl 
being  suitable  for  this  purpose.  The  stirring  apparatus  is  put  in  motion  and 
hydrogen  introduced.  The  oil  hardens  very  satisfactorily  by  this  treatment. 

*  Les  Matures  Grasses,  1914,  7,  4151 ;   J.  S.  C.  I.,  1914,  972. 
t  U.  S.  Patent  1,095,144,  April  28,  1914. 


64 


THE  HYDROGENATION  OF  OILS 


FIG.  40;. 


Humphreys  *  hydrogenates  oil  with  an  apparatus  consisting  of  a 
closed  chamber  '(Fig.  40i)  having  within  it  slightly  inclined,  sup- 
porting plates,  one  above  the  other,  and  successively  discharging  at 
their  lower  edges  onto  the  upper  portions  of  the  next  succeeding 
plate  with  means  at  the  bottom  of  the  chamber  for  collecting  the 
material  being  acted  upon  and  delivering  to  a  pump  which  conveys 
it  back  to  the  top  of  the  chamber  to  complete  the  path  of  circu^tion. 
Mandelstam  f  hardens  oil  by  a  combined  spraying  and  bubbling 

method  employing  apparatus 
as  shown  in  Fig.  40j.  A  closed 
tank  heated  by  a  steam  coil 
is  two-thirds  filled  with  oil 
carrying  a  catalyzer  in  sus- 
pension. The  pumps  shown 
on  either  side  of  the  tank 
withdraw  the  oil  and  catalyzer 
mixture  from  the  lower  part 
and  spray  it  into  the  gas  space 
in  the  upper  part  cf  the  tank. 
Hydrogen  is  admitted  by  the 
pipe  shown  in  the  middle  of  the  top  of  the  apparatus  and  is  forced 
into  the  oil  at  various  places  in  the  tank  by  means  of  sprayers  or 
distributing  devices. 

An  interesting  system  of  hydrogenating  oils  is  described  by  Me  ore.  J 
The  oil  is  fed  in  a  continuous  stream  into  the  upper  portion  of  a  closed 
chamber,  where  it  meets  a  blast  of  hydrogen  and  is  atomized.  The 
chamber  is  provided  with  a  pervious  filtering  diaphragm  containing  a 
catalyzer,  and  the  mixture  of  oil  and  hydrogen  in  excess  penetrates  the 
diaphragm  into  contact  with  the  catalyzer  whereupon  the  oil  is  satu- 
rated, and  the  hydrogenated  oil  and  the  excess  of  hydrogen  pass  into 
the  lower  portion  of  the  chamber. 

The  excess  hydrogen  may  then  be  freed  of  oil  and  re-used,  and  the  hydro- 
genated product  withdrawn  in  a  continuous  stream.  To  secure  the  greatest 
possible  active  surface,  the  catalyzer  consists  of  a  layer  of  finely-divided  or 
pulverulent  material  confined  between  layers  of  filtering  material.  It  is  stated 
to  be  difficult  to  force  a  large  body  of  oil  through  such  powdery  mass,  but, 
when  the  oil  is  atomized,  it  may  be  forced  therethrough  without  difficulty  if 
the  pressure  be  sufficient. 

Moore  finds  that  proper  results  cannot  be  obtained  after  the  particles  of  the 

*  U.  S.  Patent  No.  1,100,735,  June  23,  1914. 

t  J.  S.  C.  I.,  1914,  1162;    U.  S.  Patent  1,114,623,  October,  20,  1914 
JU.   S.   Patent   No.    1,121,860,    December   22,    1914;      1,184,480,     May    23,    1916; 
J.  S.  C.  I.,  1915,  144.     Canadian  Patent  172,839,  Oct.  31,  1916. 


METHODS  OF  HYDROGENATION 


65 


catalyzer  become  covered  with  films  of  oil,  for  the  reason  that  the  hydrogen 
is  unable  to  obtain  access  thereto,  and  hence  he  provides  for  cleaning  the  cat- 
alyzer of  the  oil  and  thereby  revivifying  the  former.  This  is  accomplished  by 
causing  the  constant  passage  of  hydrogen  through  the  catalyzer,  and  also  by 
arranging  the  nozzles  for  the  oil  and  hydrogen  in  such  manner  and  so  moving 
them  that  the  spray  is  directed  progressively  toward  restricted  areas  of  the  mass 
of  catalyzer.  Hence,  through  that  portion  of  the  catalyzer  which  at  the  moment 
is  not  receiving  the  spray,  hydrogen  is  passing  through  in  such  quantities  and 
at  such  velocity  as  to  blow  off  or  remove  the  films  or  coatings  of  oil  which 


FIG.  40fc. 

enclose  the  particles.  Thus  each  restricted  portion  of  the  catalyzer  first  receives 
the  mixture  of  oil  and  hydrogen,  and  is  then  freed  of  the  oil,  either  as  such 
or  in  saturated  or  partially  saturated  condition.  By  this  procedure  the  quantity 
of  oil  which  any  one  portion  of  the  diaphragm  and  the  catalyzer  is  receiving 
is  relatively  small,  and  the  oil  is  so  broken  up  and  mixed  with  the  hydrogen 
that  it  is  readily  carried  through  the  catalyzer  bed,  and  hydrogenated  instan- 
taneously, so  it  is  claimed.  By  regulating  the  oil  supply,  the  degree  of  solidity 
of  the  hydrogenated  product  is  adjusted  to  any  predetermined  point,  according 
to  the  use  for  which  it  is  intended. 


66 


THE  HYDROGENATION  OF  OILS 


In  Fig.  40fc,  an  apparatus  is  shown  consisting  of  a  cast-metal  casing  forming 
a  cylindrical  chamber,  transversely  divided  by  a  filter  diaphragm  containing  the 
catalyzer.  The  diaphragm  consists  'of  a  perforated  plate,  upon  which  rests 
a  layer  of  wire  cloth,  preferably  about  100  mesh.  Upon  the  wire  cloth  is  a 
thin  layer  of  suitable  inert  material,  such  as  a  matt  of  asbestos  fiber.  Upon 
the  layer  of  asbestos  is  a  thin  layer  of  the  catalyzer,  and  upon  this  is  placed 
another  layer  of  asbestos.  The  oil  and  hydrogen  are  introduced  into  the  upper 
compartment  through  down-turned  nozzles.  These  nozzles  are  so  located  that 
the  blast  of  hydrogen,  traveling  at  high  velocity,  impinges  upon  the  stream  of 
oil  flowing  from  the  nozzle  and  atomizes  the  latter,  directing  the  spray  across 
the  surface  of  the  diaphragm.  The  nozzles  revolve  and  thus  direct  the  spray 
progressively  in  a  circle  over  the  entire  surface  of  the  diaphragm. 

The  Moore  process  of  hydrogenation  used  at  the  plant  of  the  Berlin 
Mills  Company,  Berlin,  N.  H.,  is  discussed  by  Hendricks,*  who 
states  that  the  plant  is  of  a  very  highly  developed  semi-commercial 
nature  with  a  capacity  if  30,000  pounds  daily. 

The  Ney  process  of  hydrogenation  is  carried  out  with  the  appara- 
tus in  Fig.  401 

In  describing  his  process  Ney  observes  that  the  generally  accepted  theory  for 
the  explanation  of  catalytic  reactions  is  the  formation  of  certain  instable  inter- 
mediate compounds  of  the  catalyst  with  one  or  more  of  the  reagents.  In  the 
instance  of  the  catalysts,  like  nickel,  the  formation  and  decomposition  alternate 
of  a  nickel-hydrogen  compound  or  hydride  is  hypothetically  presumed.  It  is 

immaterial  for  the  purpose  of  the 
present  consideration  whether  these 
hydrides  are  stable  for  any  length  of 
time  under  certain  conditions  or 
whether  they  always  instantaneously 
are  formed,  decompose  and  are  re- 
formed. In  the  technical  application 
FIG.  40Z.  of  catalytic  reduction  the  fact  alone 

is    of    importance    that    under    certain 

favorable  conditions  the  formation  of  the  hydride  takes  place  and  subsequently 
an  exchange  or  transfer  of  the  hydrogen  atom  from  the  hydride  to  the  organic 
body.  In  considering  the  dynamics  of  this  reaction  it  is  apparent  that  the 
hydrogenation  of  organic  bodies  must  take  place  in  a  series  of  distinct  phases. 
When  the  organic  body  first  comes  in  contact  with  prepared  catalyst  in  the 
presence  of  hydrogen,  an  instantaneous  transfer  of  the  stock  of  hydrogen  already 
present  in  the  catalyst  takes  place.  Subsequently  if  the  catalyst  is  again  ex- 
posed to  the  influence  of  a  fresh  supply  of  hydrogen,  a  reformation  or  regenera- 
tion of  hydride  follows,  followed  by  a  renewed  transfer  of  hydrogen  to  fresh 
material  until  all  unsaturated  bodies  have  become  saturated  ones.  It  is,  however, 
clear  that  this  is  only  the  case  if  the  catalyzer  is  permanently  kept  free  of  the 
organic  material  or  where  the  organic  body  can  be  maintained  in  form  of  a 
true  vapor  or  gas  under  the  conditions  of  hydrogenation. 

In  case  of  organic  material  incapable  of  being  transformed  into  the  vaporous 


*J.  Ind.  Eng.  Chem.,  9,  795. 


METHODS  OF  HYDROGENATION  67 

to  gaseous  state,  entirely  different  conditions  prevail.  When  the  material,  such 
as  a  mixture  of  the  glycerides,  of  unsaturated  fatty  acids  meet  first  the  cat- 
alyzer, the  first  of  the  above  mentioned  phases  takes  place.  However,  as  the 
hydrogenated  material  and  the  excess  of  the  original  product  keep  on  flowing 
over  the  catalyzer  or  reaching  it  in  some  other  way,  these  bodies  are  not  imme- 
diately removed  as  in  case  of  a  true  vapor  or  gas,  but  rather  on  account  of 
certain  physical  properties  as  viscosity,  surface  adhesion  and  capillary  energy, 
adhere  strongly  and  tenaciously  to  the  catalyst  or  its  carrier,  thus  preventing 
or  greatly  impeding  the  reformation  of  the  hydride  due  to  the  sealing  up  of 
the  surfaces  of  the  catalyst  and  preventing  the  access  of  the  hydrogen  to  it. 
In  Ney's  process  catalyzer  is  placed  in  baskets  mounted  on  a  shaft  arranged 
to  rotate  in  a  chamber  containing  hydrogen.  Oil  is  atomized  in  the  chamber 
by  means  of  the  atomizers  shown  on  the  right  of  the  illustration,  and  the 
"oil-fog"  produced  impinges  on  the  catalyzer.  Owing  to  the  relatively  slight 
centrifugal  force  exerted  upon  the  oil-fog,  its  penetrative  properties  are  inher- 
ently good,  while  as  coagulation  of  the  oil  occurs  so  that  a  concrete  drop  or 
particle  is  produced,  then  centrifugal  action  manifests  itself  and  the  concrete  oil 
particle  is  ejected  from  the  basket  or  drum.  Hence  it  follows  that  while  the 
catalyzer  is  freely  in  contact  with  the  fog  particles  in  the  presence  of  the  hydro- 
gen gas,  the  discrete  or  concrete  particles  of  oil  are  removed  from  its  surfaces 
by  centrifugal  action,  and  thereby  the  catalyzer  is  revivified  or  prevented  from 
becoming  sealed  away  from  the  hydrogen  gas,  and  its  action  upon  the  oil  is 
constant  and  effective.  Thus,  the  reformation  of  the  hydrides  (or  other  action 
produced  by  the  contact  of  the  catalyzer  and  hydrogen),  is  continually  in  prog- 
ress. A  catalyzer  of  substantially  constant  hydrogen  (or  hydride)  content  is 
secured.* 

In  Maryott's  process  f  fats  or  fatty  acids  are  dissolved  in  some 
fat  solvent,  such  as  alcohol,  acetone,  ether,  petroleum  ether,  ben- 
zene, chloroform,  carbon  disulphide,  carbon  tetrachloride,  or  other 
fat  solvent  and  the  fat  or  fatty  acid,  while  in  the  solvent,  is  subjected 
to  the  action  of  hydrogen  in  the  presence  of  some  catalyzer,  preferably 
palladium. 

It  is  not  necessary  that  the  fatty  substance  be  completely  dissolved  in  the 
solvent,  for  triolein,  for  instance,  in  alcohol  at  a  temperature  below  that  at 
which  it  is  completely  soluble,  is  readily  reduced  in  the  presence  of  finely- 
divided  palladium.  In  general,  a  solution  containing  about  25  to  50  per  cent 
of  fat  is  preferable. 

The  process  can  be  carried  out  in  a  reaction  chamber  provided  with  an  agi- 
tator and  suitable  means  for  regulating  the  temperature  and  gas  pressure.  The 
solution  of  the  fat  or  fatty  acid  in  the  fat  solvent  containing  in  suspension  the 
catalyzer,  preferably  deposited  on  some  finely-divided  material  as  asbestos,  is 
introduced  into  the  chamber,  and  kept  agitated  to  insure  a  uniform  mixing 
with  the  catalyzer,  while  the  temperature  is  suitably  regulated,  and  the  hydro- 
gen conducted  into  the  chamber  under  appropriate  pressure.  While  the  unsat- 
urated fatty  bodies,  when  dissolved,  for  instance,  in  alcohol  or  acetone,  are 

*U.  S.  Patent  No.  1,185,704,  Juno  6,  1916. 
fU.  S.  Patent  No.   1,097,456,  May  19,   1914. 


68 


THE   HYDROGENATION  OF  OILS 


hydrogenized  in  the  presence  of  finely-divided  palladium  at  room  temperature 
under  atmospheric  pressure,  a  higher  temperature  and  a  greater  pressure  favor 
the  reduction.  After  the  reduction  has  proceeded  sufficiently  far,  as  shown  by 
tests  of  samples  withdrawn,  the  mixture  is  removed  from  the  reaction  chamber, 
the  catalyzer  separated  by  filtration,  and  the  solvent  distilled  off  either  at  atmos- 
pheric pressure  or  at  reduced  pressure,  or  without  distilling  off  the  solvent  the 
reduced  fatty  substance  may  be  largely  removed  by  cooling  and  filtering  off  the 
separated  fat. 

Instead  of  agitating  the  solution  of  the  fat  or  fatty  acid  in  the  reaction 
chamber,  the  solution  containing  the  suspended  catalyzer  can  be  sprayed  by 
means  of  an  atomizer  into  a  chamber  of  hydrogen,  and  after  sufficient  action 
the  mixture  can  be  treated  as  above  for  the  removal  of  the  catalyzer  and  the 
solvent. 


FIG.  40m. 

The  influence  of  the  solvent  in  facilitating  the  action  of  the  hydrogen  on  the 
fat  or  fatty  acid  in  solution  might  find  an  explanation  according  to  Maryott, 
in  the  better  opportunity  afforded  for  the  freer  diffusion  of  the  reacting  sub- 
stances. Maryott  states  that  benzene,  gasoline,  and  ether  are  solvents  which 
greatly  increase  the  speed  of  the  reaction. 

According  to  the  de  Jahn  process,*  oil  is  agitated  with  hydrogen 
in  one  vessel  and  then  passed  through  a  second  vessel  containing  the 
catalyst.  The  circulation  of  the  fat  is  continued  until  hydrogenation 
is  complete.  The  apparatus  used  by  de  Jahn  is  shown  in  Fig.  40m, 

*  U.  S.  Patent  No.  1,131,339,  March  9,  1915;    J.  S.  C.  I.,  1915,  434. 


METHODS  OF  HYDROGENATION  69 

the  agitating  vessel  appearing  on  the  right,  and  the  catalyzer  chamber 
on  the  left  of  the  illustration. 

The  catalyzer,  which  may  consist  of  cobalt,  palladium,  or  nickel,  is 
carried  in  thin  layers  on  an  inert  material,  such  as  porous  burnt  clay 
lumps  or  pumice  stone. 

Various  forms  of  apparatus  are  employed  by  Calvert,*  one  of  which  is  shown  in 
Fig.  40/i,  and  consists  of  a  gas-tight  inclosure  comprising  a  commingling  chamber  a, 
a  motor  chamber  e,  and  a  pipe  d  connecting  the  two.  The  liquid  to  be  treated 
such  as  oil,  is  placed  in  the  commingling  chamber  a.  The  commingling  means 
is  in  the  form  of  stirrer  blades  c  mounted  on  a  shaft  6,  which  passes  through 
the  pipe  d  and  is  driven  by  a  motor  /  located  within  the  motor  chamber  e. 
In  the  case  of  the  hydrogenation  of  oils  /  is  preferably  a  motor  of  the  induction 


FIG. 


type  so  as  to  avoid  sparking.  The  gas  which  is  to  be  commingled  with  the  oil 
is  supplied  to  the  gas-tight  inclosure  by  a  pipe  g  which  for  instance  may  be 
connected  to  the  motor  chamber  e,  the  gas  passing  from  the  chamber  through 
the  pipe  d  into  the  commingling  chamber  a.  In  the  hydrogenation  of  oils  this 
pressure  is  sometimes  fairly  high  and  hence  the  great  difficulty  associated  with 
the  prevention  of  leakage  if  the  stirring  mechanism  for  the  shaft  6  passes  through 
a  stuffing  gland.  In  the  apparatus  of  Calvert  there  are  no  packing  glands  for  any 
moving  parts  passing  through  the  walls  of  the  gas-tight  inclosure  and  consequently 
hydrogen  cannot  leak  from  the  interior  of  the  vessel.  In  order  to  prevent  vapor 
rising  to  the  motor  chamber  e  and  to  maintain  this  chamber  fairly  cool,  a  jacket  i 
through  which  water  circulates  may  be  arranged  on  the  connecting  pipe  d.  The 
finished  product  is  removed  from  the  commingling  chamber  a  by  a  pipe  k. 

Another    form  of  the  apparatus,  Fig.  40o,  has  stirrers    driven  by  an  electro- 
magnet placed  outside  of  the  hydrogenation  chamber.     On  rotation  of  the  shaft 
*U.  S.  Patent  No.  1,123,092,  Dec.  29,  1914. 


70 


THE  HYDROGENATION  OF  OILS 


carrying  the  magnet  the  stirrers  inside  the  chamber  are  actuated  by  magnetic 
action. 

Mechanical  agitation  of  the  catalyst  is  effected  by  Walter,*  through 
the  application  of  a  magnetic  field.  If  the  catalyst  itself  is  not  mag- 
netic it  is  supported  on  a  magnetic  body.  By  rapidly  making  and 
breaking  the  circuit  forming  the  magnetic  field,  fresh  parts  of  the 


FIG.  400. 


FIG.  40p. 


catalyst  can  continually  be  brought  into  contact  with  the  reacting 
substances  and  the  catalyst  can  be  moved  to  different  parts  of  the 
apparatus.  For  reactions  with  gases  the  catalyst  is  supported  pref- 
erably on  nets  or  perforated  plates  and  a  magnetic  field  is  maintained 
permanently  near  the  outlet  to  cause  the  settling  of  any  material 
carried  along  by  the  gas.  f 
By  another  method  proposed  by  Calvert  J  a  mixture  of  oil  and 

*  German  Patent  No.  295,507,  April  20,   1913;  J.  Chem.  Soc.  1918,  Abs.,  ii,  163. 
t  See  also  French  Patent  to  Walter,  No.  471,108,  October  15,  1914. 
J  J.  S.  C.  I.  1915,  434;   British  Patent  5967,  March  9,  1914;  U.  S.  Patent  1,142,668, 
June  8,  1915. 


METHODS  OF   HYDROGENATION 


71 


catalyst  is  treated  with  hydrogen  in  a  closed  vessel  containing  a  rotating 
comb-shaped  agitator  surrounded  by  a  stationary  gauze  screen,  which 
finely  subdivides  the  oil,  while  a  centrifugal  propeller  at  the  base 
flings  the  mixture  upwards  to  be  beaten  and  subdivided  again. 

Calvert  claims  that  improved  results  are  obtained  when,  in  addition  to  pres- 
sure, there  are  repeated  shocks  or  impacts  applied  to  the  oil  under  pressure. 
Such  a  shock,  it  is  alleged,  cannot  be  applied  readily  by  aid  of  a  spray. 

The  oil  is  hydrogenated  by  subjecting  a  hot  mixture  of  oil  and  catalyst  under 
pressure  and  in  the  presence  of  hydrogen  to  such  repeated  mechanical  shocks  or 
impacts.  This  may  be  effected  by  means  of  rotary  beaters.  In.  treating  oil  for 
edible  use,  it  is  important  to  avoid  decomposition  of  the  fat  and  Calvert  states 
this  can  best  be  done  by  employing  high  pressures  of  hydrogen,  as  such  high 
pressures  not  only  prevent  decomposition,  but  they  also  facilitate  the  absorption 
of  hydrogen  by  the  fat.  Pressures  up  to  and  above  250  Ib.  per  square  inch  are 
used. 


^:>uw 
o 

X 

8. 

K" 

^—- 

Absorption  -cu.f 

r> 
0  C 

o  8  1 

/ 

/ 

/ 

/ 

^ 

3                       50                    !00,                  15 
Temperature  °C 

FIG.  40g. 

The  mixture  of  oil  and  catalyst  is  supplied  to  a  closed  container,  Fig.  40p, 
of  spherical  form  to  withstand  the  high  pressures  employed,  and  fitted  with  a 
commingling  device  which  imparts  shocks  or  impacts  to  the  oil  and  catalyst. 
This  device  consists  of  a  propeller  at  the  base  and  rotary  agitators  above,  in 
the  form  of  a  comb.  These  rotary  or  moving  parts  are  mounted  on  a  shaft 
which  is  driven  by  a  motor  inclosed  in  a  casing  over  the  spherical  container. 

The  temperature  of  operation  is  chosen  with  regard  to  the  kind  of  oil  to  be 
treated.  It  will  be  found  on  trial,  Calvert  states,  that  there  is  a  compar- 
atively small  range  of  temperature  at  which  absorption  is  most  active.  The 
curve  showing  the  rate  of  absorption  and  the  temperature  follows  practically 
in  a  straight  line  till  a  certain  point  is  reached,  when  it  ceases  to  have  an 
upward  inclination  .and  passes  over  into  a  substantially  horizontal  line.  This 
curve  is  indicated  in  Fig.  40q,  which  is  the  approximate  curve  for  fish  oil. 
The  rate  of  absorption,  as  stated,  is  also  increased  with  the  pressure  and  espe- 
cially in  the  case  of  vegetable  oils  intended  for  food  purposes  the  pressure  should 
be  high  to  prevent  decomposition.  In  the  latter  case  the  pressure  should  be 


72 


THE  HYDROGENATION  OF  OILS 


above  250  Ib.  per  square  inch,  and  may  be  as  high  as  500  Ib.  to  600  Ib.  per 
square  inch.  Whale  oil  has  been  deodorized  in  twenty  minutes,  and  hydro- 
genated  to  a  hard  fat  in  fifty-five  minutes  with  the  Calvert  apparatus.  The 
approach  of  the  point  of  saturation  can  be  readily  ascertained  by  observing 
the  absorption  of  the  hydrogen  by  a  suitable  gauge  on  the  hydrogen  supply 
pipe.  With  this  apparatus  there  is  little  likelihood  of  leakage  of  hydrogen  so 
that  the  gauge  gives  a  correct  indication  of  the  rate  of  absorption. 

Pictet  *  hydrogenates  oil  by  causing  it  to  flow  by  gravitation,  with 
or  without  the  addition  of  a  catalyst,  through  a  series  of  commu- 
nicating tubes  the  walls  of  which  are  composed  of  a  catalytic  metal. 
The  inner  surface  of  the  walls  of  the  tubes  is  submitted  to  a  preliminary 
treatment  to  increase  the  catalytic  activity  of  the  metal.  Hydrogen 
is  introduced  into  the  tubes,  and  the  oil  is  subdivided  by  rotating 
devices,  which  constantly  brush  against  the  inner  walls. 


FIG.  40r. 


Details  of  the  apparatus  f  of  Birkeland  and  Devik  (see  p.  36) 
are  shown  in  the  accompanying  illustration.  Fig.  40r  is  a  hydro- 
genating  apparatus  shown  in  section.  Birkeland  and  Devik  state 
that  when  an  efficient  catalyzer,  for  instance  pyrophoric  nickel,  and 
a  good  oil  is  employed,  the  hardening  will  be  effected  in  from  one-half 
to  one  hour. 

They  observe  that  it  is  advantageous  to  employ  injectors  which  are  so  con- 
structed that  the  shape  or  thickness  of  the  oil  jet  may  be  altered,  because 
such  alterations  during  the  working  have  proved  to  be  necessary  in  order  to 
obtain  at  each  moment  the  best  possible  atomization  and  distribution  of  the 
gas  in  the  liquid.  To  obtain  this  a  member  adjustable  from  the  outside  may 
may  be  provided  in  the  injector.  The  oil  is  introduced  into  the  vessel  11  through 
adjustable  injector  nozzles  12,  so  as  to  produce  a  mixture  of  the  very  hot  oil 
with  hydrogen.  This  milky-white  mixture,  in  which  the  bubbles  of  hydrogen 
are  too  small  to  be  observed  with  the  naked  eye,  is  then  introduced  through 

*  J.  S.  C.  I.,  1915,  434;   French  Patent  No.  472,080,  July  24,  1913. 
fU.  S.  Patent  No.  1,125,259,  Jan.  19,  1915.     See  also  Nos.  1,271,575  and  1,271,570 
issued  July  9,  1918  to  Ittner. 


METHODS  OF  HYDROGENATION  73 

a  reduction  valve,  13,  into  a  larger  vessel,  14.  Birkeland  and  Devik  claim  to 
have  found  that  under  this  expansion  the  intimate  mixture  of  oil  and  hydrogen 
give 3  off  malodorous  volatile  substances  which  may  be  condensed  and  washed 
out  by  passing  the  gas  through  a  condensation  and  washing  apparatus,  15. 
This  is  stated  to  have  the  advantage  of  eliminating  several  substances  (volatile 
amines,  water,  etc.)  before  the  addition  of  the  catalyzer  so  that  on  the  one 
hand  an  unnecessary  inactivation  of  the  catalyzer  is  obviated,  while  on  the 
other  hand  hydrogen  is  consumed  only  for  the  purpose  of  hardening  the  oil 
itself  and  not  for  the  hydrogenation  of  the  volatile  bodies.  The  hydrogen  gas, 
after  having  passed  through  the  vessel,  14,  and  having  thereupon  been  puri- 
fied, is  then  again  compressed  and  brought  into  circulation  anew  by  being  intro- 
duced into  the  hydrogen  space,  18.  When  the  oil  has  in  this  manner  been 
freed  from  various  malodorous  volatile  substances  the  hardening  process  may 
be  started  by  adding  the  catalyzer  to  the  oil.  During  the  hardening  operation 
the  same  circulation  as  before  described  may  be  maintained  or  the  inlet  to  the 
expansion  tank  may  be  closed  and  the  oil  maintained  in  circulation  only  through 
the  pressure  vessel,  11. 

Some  details  of  Utescher's  process  (see  page  33)  are  found  in  U.  S. 
Patent  1,124,560,  Jan.  12,  1915,  where  the  observation  appears  that 
it  has  already  been  proposed  to  render  fish  or  train  oil  odorless  by 
subjecting  the  oil  which  is  maintained  in  motion,  to  the  action  of 
silent  electrical  discharges  in  the  presence  of  hydrogen. 

By  this  means  the  fish  or  train  oil  is  at  the  same  time  hardened,  as  the 
glycerides  of  unsaturated  fatty  acids  are  saturated  by  combining  with  hydrogen, 
and  as  particularly  the  glycerides  of  oleic  acid  are  partly  converted  into  glycer- 
ides of  stearic  acid.  Further  it  has  been  proposed  to  convert  unsaturated  fatty 
acids  or  their  glycerides  into  saturated  compounds,  by  treating  the  fatty  sub- 
stances with  hydrogen  in  the  presence  of  a  finely-divided  contact  metal  or 
catalytic  agent,  such  as  finely-divided  nickel  or  finely-divided  platinum  metals, 
and  that  it  is  his  object  to  combine  these  two  processes. 

According  to  Utescher  the  silent  electrical  discharge  is  chiefly  used  for  main- 
taining the  catalytic  or  contact  substance  permanently  active  and  for  consid- 
erably increasing  its  activity.  The  fatty  substances  are  either  mixed  with  the 
finely-divided  catalytic  agent  or  contact  substance  and  are  then  exposed  in  the 
usual  manner  in  the  form  of  a  thin  layer,  to  the  action  of  silent  electrical 
discharges  in  suitable  apparatus,  or  plates  of  the  contact  metal  or  contact  sub- 
stance are  arranged  in  a  suitable  manner  in  the  apparatus,  in  which  the  silent 
electrical  discharges  take  place.  The  rays  of  the  silent  electrical  discharges  are 
preferably  allowed  to  impinge  the  surface  of  the  contact  substance  or  catalytic 
agent. 

In  carrying  the  process  into  effect,  apparatus  of  the  type  in  which  the  dis- 
charge itself  is  prevented  from  coming  into  direct  contact  with  the  fatty  sub- 
stances, so  that  solely  the  chemically-active  rays  of  the  silent  discharges  come 
into  action  may  be  employed;  for  instance  Utescher  states,  the  mercury  lamp 
may  be  used.  The  rays  from  such  a  source  are  allowed  to  impinge  on  the 
surface  of  the  contact  substance.  By  means  of  this  combined  process  Utescher 
declares  it  is  possible  to  effect  combination  with  the  hydrogen,  while  the  com- 
bined effect  exceeds  the  effect  of  the  total  of  the  two  agents  acting  separately. 


74  THE  HYDROGENATION  OF  OILS 

The  process  renders  it  possible  to  effect  the  saturation  of  the  unsaturated  fatty 
acids  and  their  glycerides,  without  mixing  finely-divided  contact  metal  therewith. 
so  that  the  expense  incurred  by  the  recovery,  of  the  contact  metal  from  the 
oil  and  by  the  regeneration  of  the  contact  substance  is  saved.  When  using 
metal  plates  in  carrying  out  the  process  it  is  sufficient  to  heat  the  plates  from 
time  to  time.  The  process  may  also  be  carried  into  effect  by  coating  the  glass 
tubes  in  which  the  silent  discharge  takes  place  with  a  thin  layer  of  contact 
metal  and  by  arranging  plates  of  contact  metal  in  the  reaction  space. 

The  action  of  the  electric  rays  on  contact  metals  is  such  that  catalyzers  are 
said  to  retain  an  increased  activity  even  after  the  oil  treatment  rendering  it 
possible  to  also  carry  the  process  into  effect,  by  first  subjecting  the  metal  to 
the  action  of  electric  rays  and  by  using  the  thus  prepared  metal  as  a  contact 
substance  during  the  treatment  of  the  oil  with  hydrogen. 

In  order  to  render  the  metal  active  it  is  subjected  to  a  cathode  atomization 
treatment  in  an  atmosphere  of  hydrogen.  The  method  of  procedure  is  as  fol- 
lows: the  metal  plate  which  is  to  serve  as  contact  substance  or  catalytic  agent 
is  used  as  cathode  in  the  atomization  process.  A  pin  of  metal  is  used  as  anode. 
The  chamber  is  first  evacuated,  whereupon  hydrogen  which  has  previously  been 
carefully  dried  is  introduced.  The  electric  current  is  then  passed  through  while 
at  the  same  time  a  continuous  slow  stream  of  hydrogen  traverses  the  apparatus. 
During  the  evacuation  care  must  be  taken  that  no  traces  of  oil  or  fat  vapor 
penetrate  into  the  vessel,  as  these  would  deposit  on  the  metal  and  cause  dif- 
ficulties. As  by  this  treatment  a  high  chemical  activity  is  sa  d  to  be  imparted 
to  the  metal,  air  must  not  be  allowed  to  enter  the  vessel  immediately  after  the 
completion  of  the  atomizing  operation  as  this  might  cause  oxy-hydrogen  gas 
explosions.  The  hydrogen  must  first  of  all  be  displaced  by  nitrogen.  As  soon 
as  the  activity  of  the  metal  has  disappeared,  after  having  burnt  off  the  fat, 
it  need  only  be  subjected  to  a  renewed  treatment  as  above. 

Walker  *  claims  the  combined  application  of  a  high-tension  elec- 
trical discharge  and  catalytic  material  in  the  hydrogenation  of  oils. 

According  to  his  method  a  receptacle  is  provided  containing  a  hollow  metallic 
plate  which  is  capable  of  being  heated,  on  which  plate  the  catalytic  agent  is 
supported.  Nickel  or  nickel  oxide  is  recommended  as  catalytic  material.  The 
hollow  plate  also  serves  as  an  electrode.  Near  this  electrode  is  mounted  a  second 
electrode.  Oil  is  projected  against  the  heated  plate  by  means  of  hydrogen 
acting  as  an  atomizing  agent,  the  finely-divided  oil  particles  being  allowed  to 
impinge  upon  the  heated  plate  while  an  electrical  discharge  is  maintained  be- 
tween the  electrodes.  Referring  to  Fig.  40s,  1  is  the  receptacle  and  2  the  hollow 
metallic  plate  provided  with  an  inlet  pipe  3  and  an  outlet  pipe  4  by  means  of 
which  superheated  steam  is  passed  through  the  hollow  plate.  The  plates  5,  5', 
together  constitute  a  compound  terminal  electrode  .cooperating  with  the  electrode 
2.  6  is  a  source  of  high-tension  current.  One  of  the  leads  7  from  this  source 
connects  with  the  electrodes  5,  5',  while  the  other  lead  8  connects  with  the 
hollow  plate  2.  An  injector  10  is  maintained  at  9  in  the  walls  of  the  receptacle. 
By  means  of  this  injector,  hydrogen  and  oil  under  high  pressure  is  caused  to 
impinge  upon  the  plate  2,  contacting  with  the  finely-divided  catalytic  agent. 
The  latter  may  be  supported  by  means  of  channels  or  corrugations  in  the  face 

*Chem.  Abs.  1915,  729;    U.  S.  Patent  No.  1,123,962.  January  5,  1915. 


METHODS  OF  HYDROGENATION 


75 


of  the  plate.  The  high-tension  electrical  discharge  passes  from  one  electrode 
member  to  the  other,  through  the  space  between  the  electrodes,  acting  on  the 
hydrogen  and  finely-divided  oil  traversing  this  space.  Walker  claims  that 
reaction  results  through  the  combined  influence  of  the  electrical  discharge  and 
the  catalytic  agent.  It  is  stated  by  Walker  that  hydrogenated  oil  is  secured  in 
this  manner,  without  the  injurious  results  which  often  follow  from  subjecting 
oil  to  "  the  extended  application  of  heat." 

McElroy*  describes  a  process  of  hydrogenating  oils  with  apparatus 
shown  in  Figs.  402  and  40w,  as  follows: 

A  tank  is  provided  with  a  steam-heating  coil  and  hydrogen  inlets 
and  outlets.  In  the  top,  on  the  right-hand  side,  is  an  oil-charging 


Steam  Outlet 


FIG.  40s. 

pipe.  On  the  top  is  situated  a  housing  containing  a  pump  or  blower, 
the  latter  being  arranged  to  draw  in  hydrogen  from  a  point  just  below 
the  top  of  the  tank  and  to  propel  it  to  the  bottom.  The  hydrogen 
discharges  at  that  point  through  a  revolving  distributer  shown  in 
Fig.  40w.  There  is  a  pressure-equalizing  opening  in  the  housing  floor. 
The  tank  is  filled  with  oil  to  the  level  indicated.  A  screen  is  placed 
above  the  oil-level  to  serve  to  break  up  bubbles  or  foam.  Nickel 
on  pumice  or  coke  is  suspended  in  the  oil  and  the  contents  of  the 
tank  are  raised  to  150°  to  200°  C.  A  pressure  of  hydrogen  of  five 
or  six  atmospheres  is  attained  and  the  gas  is  caused  to  circulate  from 
top  to  bottom  by  means  of  the  blower  in  the  housing.  The  discharge 
of  hydrogen  through  the  distributer  causes  the  latter  to  rotate  and 
sweep  the  bottom  free  of  catalyzer. 

*U.  S.  Patent  No.  1,157,993,  October  26,  1915.  ' 


76 


THE  HYDROGENATION  OF  OILS 


In  a  hydrogenation  system  involving  the  bubbling  of  hydrogen 
gas  through  a  body  of  oil  carrying  catalytic  material  in  suspension, 
the  hydrogen  may  be  transferred  from  one  gas-holder  to  another, 
passing  through  the  oil,  while  undergoing  such  transference,  according 
to  Ellis.*  In  order  to  secure  a  better  utilization  of  the  hydrogen,  it 
may  be  preheated  by  passing  through  a  heat  interchanger  through 
which  hot  hydrogen  issuing  from  the  converter  is  conveyed. 


Hydrogen 
Outlet* 


Hydrogen 
Inlet 


Steam 
Outlet 


Steam 
Inlet 


FIG.  40*. 

An  apparatus  has  been  devised  by  E.  Emmet  Reid  f  and  used  for 
the  study  of  catalytic  hydrogenation,  but  may  serve  for  the  study 
of  any  reaction  in  which  a  gas  is  to  be  brought  into  intimate  contact 
with  a  liquid  under  constant  conditions.  The  problem  is  to  intro- 
duce a  high-speed  stirrer,  inlet  and  outlet  tubes,  and,  possibly,  a 
sampling  tube  through  a  comparatively  small  stopper  and  to  render 
the  whole  gas-tight  for  both  increased  and  reduced  pressure.  The 
apparatus  is  shown  in  the  sketch  in  section,  Fig.  4O. 

*U.  S.  Patent  No.  1,247,095,  November  20,  1917. 
t  J.  Am.  Chem.  Soc.,  1915,  2112. 


METHODS  OF  HYDROGENATION 


77 


The  bearing,  AC,  is  made  of  two  pieces  of  steel  rod,  AB,  and  BC,  0.5  and  1.5 
in.  long,  respectively.  Roth  of  these  have  a  f-in.  hole  drilled  longitudinally 
through  them,  then  the  longer  one  is  drilled  out  to  a  size  of  about  ^  for  most  of 
its  length,  i.e.,  from  B  to  D.  The  shorter  piece  is  turned  down  for  half  its 
length  till  it  fits  closely  into  the  other,  so  that  a  double  bearing  is  formed,  with 
an  enlarged  cavity  in  the  central  portion.  The  two  parts  are  assembled  and 
channels  about  r?  by  ^  in.  are  cut  in  opposite  sides  as  shown  at  J  and  K  in 
cross-section  in  Fig.  4Qw.  Care  must  be  taken  that  the  channels  do  not  cut 
through  the  walls  of  the  cavity.  The  ^  brass  tubes  that  are  used  for  the 
gas  inlet  and  outlet  tubes  are  laid  in  these  channels  which  are  then  filled  with 


FIG.  40w. 


FIG.  40z. 


FIG.  40y. 


solder,  the  solder  more  than  filling  the  channels.  The  excess  of  solder  is  turned 
off  in  the  lathe  so  that  the  whole  is  a  perfect  cylinder  externally  and  adapted  to 
make  a  tight  joint  when  passed  through  a  cork. 

The  stirrers  may  be  of  any  suitable  form,  but  the  Witt  centrifugal  stirrer 
shown  is  one  of  the  best,  as  when  run  at  high  speed,  it  effects  very  thorough 
mixing.  The  stirrer  may  be  made  of  glass  and  fastened  to  the  shaft  by  a  bit 
of  wire  which  passes  through  a  hole  in  the  shaft  and  through  holes  in  the 
stirrer.  The  shaft,  S,  is  of  i-in.  drill  rod  and  carries  a  pulley  of  suitable  size. 
The  inlet  and  outlet  tubes  are  bent  as  shown  and  carry  enlargements  so  as  to 
make  convenient  joints  with  rubber  tubing. 

The  bearing  passes  through  a  hole  in  a  0.5-in.  rod,  F,  and  is  held  in  place 
by  a  set  screw,  G.  This  rod  is  conveniently  clamped  to  a  laboratory  iron  stand. 

To   assemble   the   apparatus,   the  shaft  is  pushed  a  short   distance  into  the 


78  THE  HYDROGENATION  OF  OILS 

bearing  from  the  bottom  and  mercury  is  poured  in.  The  shaft  is  then  pushed  on 
through,  causing  the  excess  of  mercury  to  overflow  and  leaving  the  cavity  in 
the  bearing  filled  with  mercury.  Thus  a  gas-tight  mercury  seal  is  formed  which 
is  tight  no  matter  how  fast  the  shaft  rotates.  To  make  a  stuffing-box  gas-tight 
would  require  so  much  pressure  that  the  rotation  of  the  shaft  would  be  hindered. 
The  mercury  seal,  though  tight,  offers  no  resistance  to  the  motion  of  the  shaft. 
This  seal  is  tight  against  either  excess  or  -diminished  pressure  for  moderate 
pressures.  The  apparatus  in  use  proved  to  be  gas-tight  under  a  pressure  of 
3  ft.  of  water.  The  shaft  must  fit  the  bearings  very  accurately  to  avoid  danger 
of  loss  of  mercury,  but  little  trouble  has  been  met  with  in  this  respect.  Lu- 
brication is  accomplished  by  placing  a  drop  of  oil  above  and  below  the  bearings 
and  working  the  shaft  up  and  down  a  few  times.  This  should  be  done  each 
time  the  apparatus  is  used. 

In  case  it  is  desired  to  take  out  samples  during  the  course  of  the  reaction, 
the  bearing  is  cut  from  somewhat  larger  rod,  and  a  hole  is  drilled  through 
the  assembled  bearing,  to  one  side,  as  shown  in  section  at  H  in  Fig.  4Qx.  This 
hole  is  stopped  by  a  plug  lubricated  with  oil.  For  taking  out  a  sample,  a  piece 
of  0.25-in.  glass  tubing  is  drawn  out  to  a  capillary  about  6  in.  long.  This  is 
passed  down  through  the  hole  in  the  bearing  and  the  desired  amount  of  liquid 
drawn  out.  A  hole  is  drilled  in  the  web  of  the  pulley  so  that  it  can  be  brought 
over  the  hole  in  the  bearing  and  allow  the  capillary  to  pass.  In  studying  the 
velocity  of  the  reaction,  the  time  is  taken  till  the  moment  that  the  stirrer  is 
stopped.  Taking  out  a  sample  requires  about  one  minute.  The  time  for  the 
next  period  is  taken  from  the  moment  that  the  stirrer  is  again  started.  Exper- 
iments have  shown  that  reactions  of  this  sort,  depending  on  stirring,  stand 
practically  still  when  the  stirrer  is  not  in  operation. 

The  size  apparatus  here  described  has  proved  extremely  useful  for  small-scale 
work  of  a  variety  of  kinds.  Obviously,  the  same  plan  might  be  used  for  appa- 
ratus for  larger  operations.  The  flask  is  heated  to  any  desired  temperature  by 
being  placed  in  a  suitable  bath.  Temperatures  up  to  220°  have  been  used. 
The  stirrer  has  been  run  by  an  electric  motor,  a  rubber  band  serving  as  a 
convenient  belt.  Speeds  of  3000  to  4400  revolutions  per  minute  have  been  ob- 
tained without  difficulty. 

Higgins  *  effects  the  reduction  of  unsaturated  compounds  in  the 
presence  of  a  metallic  formate,  without  employing  gaseous  hydrogen. 

In  carrying  the  method  into  effect  in  its  application  to  unsaturated  fatty 
acids  or  their  esters,  these  bodies  are  intimately  mixed  with  the  salt  of  formic 
acid  and  a  catalytic  substance  and  the  mixture  is  placed  in  a  vessel  capable  of 
being  rendered  gas-tight  and  provided  with  an  agitator. 

The  contained  air  is  preferably  exhausted  from  the  vessel  or  displaced  by 
a  non-oxidizing  gas,  such  as  carbon  monoxide,  nitrogen,  carbon  dioxide,  or  hydro- 
gen and  the  temperature  then  carefully  raised  when  the  reaction  takes  place, 
which  may,  for  example,  be  represented  thus: 


The  end-products  vary  with  the  formate  used,  that  is,  with  some  formates, 
the  resulting  metallic  carbonate   is  unstable  and   carbon  dioxide  is  evolved  as 
*U.  S,  Patent  1,170,814,  Feb.  8,  1916. 


METHODS  OF  HYDROGENATION  79 

well  as  carbon  monoxide.  Owing  to  I  lie  evolution  of  carbon  dioxide  or  carbon 
monoxide  or  both,  considerable  pressures  are  generated. 

Higgins  suggests  the  following: 

1.  Nickel  formate  as  the  reducing  agent  and  the  catalyst.  2.  Zinc  formate 
as  the  reducing  agent  together  with  a  known  catalyst.  3.  Zinc  formate  as  the 
reducing  agent  admixed  with  palladium  chloride  which  under  the  conditions  of 
working  is  converted  into  a  catalytic  substance  by  the  action  of  the  zinc  formate. 

The  heating  must  be  conducted  with  care,  as  local  superheating  may  cause 
spontaneous  formation  of  oxalate  from  the  formate  and  is  liable  to  produce 
explosion.  For  this  reason  the  apparatus  must  be  provided  with  necessary  safety 
devices. 

The  reaction  can  be  conducted  practically  quantitatively,  but  for  commercial 
purposes  an  excess  of  the  reagent  over  the  theoretical  amount  necessary  is  pref- 
erably employed.  The  materials  taking  part  in  the  action  should  be  dry. 

The  temperature  may  vary  with  the  formate  or  mixture  of  formates  or  other 
reagents  employed,  but  in  general  may  be  in  the  neighborhood  of  20°  below 
the  point  at  which  the  formate  used,  spontaneously  decomposes  to  the  oxalate 
u  ider  the  pressure  existing  in  the  apparatus  at  the  time  of  so  heating. 

Experiments  by  Kalnin  reported  by  Bergius  *  have  shown  that 
hydrogenation  is  effected  by  heating  oleic  acid  with  alkali  at  300°  C.  in 
hydrogen  under  a  pressure  of  thirty  atmospheres. 

As  the  process  is  not  a  catalytic  one,  it  is  independent  of  the  purity  of  the 
oil  or  the  hydrogen.  Simultaneous  hydrogenation  and  saponification,  in  the  ab- 
sence of  catalytic  agents  Bergius  believes  will  probably  prove  a  cheaper  process 
than  that  in  use.  Commenting  on  this  process,  the  author  f  observes  that  it 
is  proposed  to  put  this  hydrogenated  and  more  or  less  saponified  product  directly 
into  the  soap  kettle  and  work  it  up  into  soap.  The  high  gas  pressure  required 
is  a  drawback  from  the  commercial  standpoint. 

Baibe  and  De  Paoli  J  describe  a  process  for  the  transformation 
of  liquid  into  solid  fatty  acid,  which  is  carried  out  in  the  following 
manner : 

Oleic  acid  is  introduced  into  a  suitable  lead-lined  apparatus  provided  with  a 
stirring  device  and  a  lead  coil,  which  latter,  by  means  of  a  two-way  cock,  may 
be  caused  to  act  either  as  a  heater  or  as  a  refrigerator.  The  temperature  is 
held  below  40°  C.,  and  equivalent  molecular  quantities  of  concentrated  sulphuric 
acid  of  66°  Be.  are  introduced  and  stirring  is  continued  until  development  of 
sulphurous  anhydride  ceases.  By  these  means  the  transformation  of  the  oleic 
acid  into  sulpho-iso-oleic  and  sulpho-oxystearic  acids  is  effected,  which  acids  are 
decomposed  by  simple  boiling  in  water  into  sulphuric  acid.  It  happens,  how- 
ever, that  during  the  long  boiling  in  the  presence  of  sulphuric  acid,  necessary  to 
decompose  the  sulpho-acids,  the  iso-oleic  and  oxystearic  acids  are  dehydrated, 
thus  giving  the  corresponding  lactones  and  anhydrides.  These  have  a  relatively 
low  melting-point  (about  25°  C.).  It  is,  therefore,  necessary  to  restore  the  water 

*Zeitsch  f.  angew.  Chem.,  1914,  524. 
t  Oil,  Paint  and  Drug  Reporter,  October  26,  1914,  18. 
I  British  Patent  No.  24,837,  May  5,  1908. 


80  THE  HYDROGENATION  OF  OILS 

to  the  anhydrides  and  convert  them  again  into  acids,  which  is  easily  effected 
by  saponification.  The  mixture  is  saponified  by  ammonia  and  treated  with  cold 
water  in  order  to  separate  the  oleic  acid.  The  ammonia  used  for  the  saponifi- 
cation is  eventually  recovered  by  boiling.  By  proceeding  in  this  manner  Barbe 
and  De  Paoli  have  obtained  from  oleic  acid  as  much  as  65  per  cent  of  fatty 
acids  having  a  melting-point  of  70°  C. 

The  benefits  to  Germany  of  the  hydrogenation  process  are  referred  to  in  an 
article  by  Hugo  Schweitzer,*  who  states  that  the  cheap  and  practical  methods 
which  were  evolved  by  the  military  authorities  for  the  generation  of  hydrogen 
are  now  utilized  in  one  of  the  industries  which  has  recently  become  of  the 
highest  importance,  namely,  the  manufacture  of  what  are  called  "hardened  oils 
and  fats."  By  treatment  with  hydrogen,  oils  and  fats  in  the  liquid  state  are 
converted  into  solid  materials,  which  usually  command  a  higher  price  for  tech- 
nical purposes,  such  as  the  manufacture  of  soap,  etc.;  and  low-class  fatty  sub- 
stances, which  are  not  fit  to  be  eaten  on  account  of  their  appearance  or  odor 
may  be  transformed  into  valuable  food  materials.  It  must  also  be  noted  that 
the  cheap  production  of  hydrogen  is  one  of  the  prominent  features  in  the  man- 
ufacture of  sulphate  of  ammonium  according  to  the  Haber  process.  Thus  the 
manufacture  of  hydrogen,  while  originated  for  military  purposes,  he  claims  is  help- 
ing to  feed  the  nation  by  providing  new  edible  substances,  on  the  one  hand,  and 
a  new  source  for  fertilizers  on  the  other. 

A  laboratory  method  for  the  hydrogenation  of  oleic  acid  is  described 
by  Dubovitz  f  The  hydrogen  employed  is  prepared  from  arsenic- 
free  zinc  and  is  purified  by  passing  it  successively  through  a  mixture 
of  ferric  oxide  and  sawdust,  potassium  bichromate  and  sulphuric 
acid,  sodium  hydroxide  solution,  a  tube  containing  palladium,  and 
concentrated  sulphuric  acid.  Catalyzer  is  prepared  by  dissolving 
50  grs.  of  nickel  nitrate  in  hot  water,  adding  pumice  stone  washed 
previously  with  hydrochloric  acid  and  ignited,  evaporating  the  mix- 
ture and  igniting  the  residue  in  a  nickel  basin  until  all  nitric  acid  has 
been  expelled.  The  ignited  residue  is  then  packed  into  a  tube  163 
cm.  in  length.  Oleic  acid,  dried  previously  at  110°  C.,  is  contained 
in  a  flask  connected  with  one  end  of  the  tube.  The  air  is  exhausted 
from  the  whole  apparatus,  and  hydrogen  is  passed  through  the  oleic 
acid  heated  at  270°  C.  The  tube  containing  the  catalyst  is  heated 
at  300°  to  350°  C.,  the  nickel  oxide  therein  having  been  reduced  in  a 
current  of  hydrogen  under  reduced  pressure  at  100°  C.  The  hydrogen 
bubbling  through  the  oleic  acid  carries  with  it  a  quantity  of  oleic  acid 
vapor  (a  low  pressure  being  maintained  in  the  apparatus)  and  the 
gaseous  mixture  passes  into  a  tube  containing  the  catalyzer,  where 
hydrogenation  of  the  oleic  acid  takes  place. 

Successful  results  are  said  to  depend  on  (1)  the  purity  of  the  reagents 

*  Popular  Science  Monthly,  December,   1914,  587. 

tSeifen.  Ztg.,  1915,  304;    J.  Chem.  Soc.,  1915,  1049;    J.  S.  C.  I.,  1916,  127. 


METHODS  OF  HYDROGENATION 


81 


used  in  making  catalyzer.  (2)  The  construction  of  apparatus.  (3) 
The  skill  and  experience  of  the  chemist. 

The  distillation  of  fatty  acids  by  means  of  hydrogen  as  carried 
out  by  Dubovitz  is  not  regarded  by  Normann  as  having  any  features 
of  novelty.* 

Robson  f  advances  the  interesting  statement  that  there  is,  "as  the  natural 
consequence  of  the  inconclusive  litigation  which  has  cost  thousands  of  pounds 
and  has  been  practically  settled  out  of  court,  so  far  as  it  has  been  settled,  a 
great  deal  of  secrecy  connected  with  the  processes  and  such  printed  accounts 
of  the  processes  and  so  fir  as  are  permitted  to  appear  in  technical  literature 
are  carefully  non-commital.  Many  stories  are  told  as  to  the  way  in  which 
the  nickel  is  used.  Some  say  it  is  used  as  dust,  some  that  the  oil  is  forced 
through  tubes  packed  with  thin  nickel  wires  parallel  to  the  length  of  the  tube, 
others  again  that  the  nickel  itself  is  made  into  tubes,  forming  long  circular 
worms,  which  are  supplied  with 
the  necessary  heat  from  outside, 
or  through  which  the  already- 
heated  oil  is  passed.  No  one 
knows  except  the  superior  officers 
of  the  factory." 

Contrary  to  the  observa- 
tions of  others,  Arnold  J 
asserts  that  in  hydrogenat- 
ing  fats  and  oils  it  has 
been  found  that  the  mere 
passing  of  the  hydrogen 
through  the  fat  or  oil  does 
not  cause  the  gas  to  be 
readily  absorbed,  and  that 
a  more  intimate  mixing  will 
greatly  reduce  the  time  re- 
quired to  produce  the  de- 
sired reduction. 

The  apparatus  illustrated  in 
Fig.  40>/  is  stated  to  be  particu- 
larly desirable  for  producing  the 
required  intimate  mixture  and 
to  greatly  reduce  the  time  re- 
quired for  the  treatment.  The 

mixing  of  the  oil  with  the  gas  is  accomplished  by  imparting  a  rotary  motion 
to  the  oil  in  the  lower  portion  of  the  tank  and  causing  the  whirling  liquid  to 
be  thrown  upwardly  into  the  space  occupied  by  the  gas,  by  means  of  blades 

*Seifen.  Ztg.,  1915,  398. 

t  Drugs,  Oils  and  Paints,  1914,  211. 

JU.  S.  Patent  No.  1,181,205,  May  2,  1916. 


FIG.  4%. 


82 


THE  HYDROGENATION  OF  OILS 


or  deflectors  which  depend  into  the  liquid.  The  oil  is  thrown  violently  against 
the  top  of  the  tank  so  that  it  is  broken  up  and  descends  through  the  gas  space 
in  a  shower,  thus  causing  all  portions  of  the  liquid  to  come  into  intimate  contact 
with  the  gas. 

Hoehn*  considers  agitation  of  fatty  material  in  the  hydrogenation 
process  to  be  undesirable. 

He  observes  that  violent  agitation  of  the  fatty  material  or  oil  possesses  marked 
disadvantages,  chief  among  which  may  be  mentioned  the  bubbling  of  the  hydro- 
gen in  or  through  the  oil  or  fatty  material,  and  that  the  best  results  are  ob- 
tainable by  subjecting  a  mass  or  "lake"  of  the  fatty  material  or  oil  having 
the  finely-divided  catalytic  agent  in  suspension,  and  having  a  relatively  large 
exposed  area  or  surface  and  a  substantial  depth,  to  the  action  of  an  atmosphere 
containing  hydrogen.  In  Fig.  402  a  tight  housing  encloses  a  series  of  pans 


Pump 


Oil  Mel- 


Pump 


Hydrogen 
Outlet 


FIG.  402. 


in  which  the  oil  is  exposed  to  the  gas.  The  oil  enters  the  lower  pan  and  is 
pumped  successively  to  the  intermediate  and  upper  pans,  finally  returning  to 
the  lower  pan.  The  saturated  oil  may  be  drawn  off  from  any  one  of  the  pans 
through  outlets  near  the  bottom  (shown  in  the  drawing  midway  of  the  pan). 

For  hydrogenating  oils,  Lane  f  proposes  apparatus  consisting  of 
a  vertical  cylindrical  vessel  which  is  heated  by  means  of  a  steam 
jacket  or  otherwise.  Beaters  rotating  horizontally  round  a  central 
vertical  shaft,  alternate  with  annular  sloping  shelves  on  the  sides 
of  the  vessel,  so  that  the  oil  entering  at  the  top  is  alternately  sprayed 
outwards  to  the  sides  and  guided  to  the  center  of  the  beaters  next 
below,  and  so  on  until  it  reaches  the  bottom;  it  is  then  pumped  again 
to  the  top  of  the  vessel,  J 

*U.  S.  Patent  No.  1.189,817,  July  4,  1916. 

t  British  Patent  No.  968,  Jan.  21,  1915;   J.  S.  C.  I.,  1916,  642. 

JS«e  also  French  Patent  No.  481,504,  Dec.  13,  1916;  Chem.  Abs.,  1917,  3122. 


METHODS  OF  HYDROGENATION 


83 


De  Hemptinne's  process  for  eliminating  the  odors  of  fish  oils  * 
consists  in  submitting  the  oil  to  the  action  of  the  silent  electric 
discharge  in  an  atmosphere  of  hydrogen. 

The  hydrogen  is  fixed  by  the  oil  and  after  a  sufficiently  prolonged  action  of 
the  silent  discharge,  the  characteristic  odor  is  gradually  modified  and  disappears. 
At  the  same  time,  the  oil  becomes  thicker.  The  latter  fact  is  due  not  only 
to  the  fixation  of  the  hydrogen,  but  also  to  a  conversion  of  the  oil  under  the 
influence  of  the  silent  discharge.  The  elimination  of  the  odor  of  fish  oil  may 
however,  be  effected  in  any  gaseous  atmosphere:  (1)  because  the  oil  is  modified 
by  the  action  of  the  silent  discharge,  independently  of  the  action  of  hydrogen 
introduced  from  an  outside  source;  (2)  because  the  silent  discharge  always  de- 
composes some  of  the  oil,  so  that  more  or  less  hydrogen  is  evolved,  which  is 
again  fixed  by  the  oil.  In  this  way,  even  when  operating  with  other  gas,  there 
is  still  an  effect  due  to  hydrogen.  Analysis  has  shown  that  after  some  time, 
when  operating  with  air,  the  gaseous  mixture  was  composed  as  follows:  10  per 
cent  of  carbon  dioxide,  20  per  cent  of  hydrogen, 
and  70  per  cent  of  nitrogen.  The  conclusion 
is  that  the  elimination  of  the  odor  of  fish  may 
be  effected  in  any  atmosphere;  but  it  is  effected 
more  rapidly  and  above  all,  more  efficiently,  in 
an  atmosphere  of  hydrogen.  Fig.  4Qaa  shows 
apparatus  used  by  de  Hemptinne. 

A  quantity  of  the  oil  is  introduced  into  a 
cylinder,  A,  in  which  are  arranged  on  a  shaft  a 
series  of  parallel  plates,  alternately  of  metal  B 
and  of  glass,  or  other  insulating  material,  C. 
These  plates  are  several  millimeters  distant  from 
each  other.  The  metal  plates  of  odd  numbers 
in  the  series  are  connected  together  and  with 


FIG.  4Qaa. 


one  of  the  poles  of  a  source  of  electricity  by  a  wire,  F;  similarly,  the  plates  of 
even  numbers  are  connected  together  and  with  the  other  pole  by  a  wire,  G. 

The  cylinder  is  rotated  by  means  of  a  pulley,  D,  and  owing  to  a  number 
of  gutters  g  fixed  to  the  interior  of  its  wall,  the  oil  is  continually  sprinkled  over 
the  upper  part  of  the  plates  and  thus  forms  on  them  a  thin  and  mobile  layer. 
The  cylinder  being  filled  with  hydrogen,  for  instance,  the  silent  electric  dis- 
charge is  caused  to  pass.  The  gas  is  fixed  by  the  oil  and  gradually  removes  its 
odor.  From  time  to  time  the  apparatus  is  stopped  to  introduce  a  fresh  quan- 
tity of  hydrogen  corresponding  with  the  gas  that  has  been  fixed.  The  apparatus 
is  provided  with  the  cocks  necessary  for  the  introduction  of  gas  and  for  the 
withdrawal  of  the  oil. 

Solomonoff  |  sets  forth  a  process  of  hardening  fats,  stearic  acid, 
palmitic  acid  and  other  fatty  acids,  naphtha  acids,  commenly  known 
as  sludge  acid,  waxes  and  the  like,  the  object  of  which  besides  raising 
the  melting-point  is  to  make  the  material  amorphous  so  that  it  may 
be  used  for  the  manufacture  of  candles;  also  for  the  purpose  of  render- 

*  U.  S.  Patent  No.  852,662,  May  7,  1907. 

t  J.  S.  C.  I.,  1911,  1125;  U.  S.  Patent  No.  1,002,186,  August  29,  1911. 


84  THE  HYDROGENATION  OF  OILS 

ing  stearic  acid  and  similar  materials  harder,  so  that  they  may  be 
used  for  insulating  and  other  purposes.  To  this  end,  the  fatty  material 
is  treated  with  anhydrous  ammonia  or  other  anhydrous  alkali. 

An  example  is  as  follows:  Powdered  fatty  acids  are  mixed  with  ammonia, 
by  passing  through  the  fatty  acids  a  stream  of  ammonia  gas,  or  they  are  mixed 
with  dry  alkalies  or  salts  of  alkalies  for  five  or  six  hours.  If  salts  of  volatile  acids 
are  used,  they  give  off  the  acids  and  form  dry  salts  of  fatty  acids.  These  salts 
are  thus  mixed  with  uncombined  free  fatty  acids.  If  salts  of  weak  non-volatile 
acids — for  instance,  ammonium  borate — are  used,  they  form  the  same  salts  of  fatty 
acids.  The  resulting  salts  can  be  separated  from  free  boric  acid  by  melting  the 
product;  boric  acid  goes  to  the  bottom.  The  quantities  of  alkalies  used  are  dif- 
ferent according  to  their  nature  and  to  the  desired  product.  Dry  ammonia  may 
be  used  in  amounts  ranging  from  0.5  to  4.55  per  cent.  The  more  ammonia  or 
salts  used,  the  higher  the  melting-point  of  the  resulting  fatty  body. 

Derivatives  of  trimethylamine,  applicable  in  the  manufacture  of 
soaps,  candles,  and  in  general  as  a  stearine  substitute,  are  prepared 
according  to  Herzmann  *  by  allowing  trimethylamine  to  act  upon 
the  chlorohydroxy  fatty  acids  or  sulphuric  acid  esters  of  hydroxy- 
fatty  acids,  such  as  Turkey  red  oil,  and  then  the  reaction  mixture  is 
heated  under  pressure  to  about  120°. 

The  union  of  unsaturated  fats  with  trimethylamine  by  the  Herzmann  method 
is  facilitated  by  pyridine  or  copper  reduced  from  the  oxide  on  an  asbestos  sup- 
port. Soaps  prepared  from  the  fatty  product  are  of  good  quality.  The  process 
yields  fats  of  high  melting-point  and  the  investment  for  plant,  in  comparison 
to  that  required  for  hydrogenation,  is  very  low.f 

De'Conno  J  observes  that  the  action  of  ammonia  or  fatty  aromatic  amines  on  the 
higher  fatty  acids  has  never  received  careful  scientific  study,  although  some  tech- 
nical experiments  have  been  made  on  the  action  of  ammonia  on  fats.  In  ethyl 
alcohol  under  pressure  ammonia  decomposed  glycerides  to  give  the  amides.  Some 
patents  have  been  taken  out  for  the  formation  of  anilides,  by  the  action  of  aniline 
on  fats,  in  this  way.  However,  no  systematic  study  of  the  formation  and  prop- 
erties of  the  numerous  amides  of  higher  fatty  acids,  with  the  idea  of  finding  deriva- 
tives having  properties  more  useful  for  identification  than  those  previously  known, 
had  been  carried  out.  De'Conno  obtained  solid  products  which  were  well  crys- 
tallized and  easily  purified,  by  the  following  method  of  preparation.  Equimolecular 
amounts  of  higher  fatty  acids  and  aromatic  amine  are  intimately  mixed  and  heated 
in  a  sealed  tube  at  230°  for  five  hours  after  evacuation  with  a  mercury  pump.  After 
cooling  the  crystalline  mass. is  purified  by  crystallization  from  96  per  cent  ethyl 
alcohol,  after  treatment  with  animal  charcoal.  In  this  way  the  amide  is  obtained 
as  white  needle-like  crystals  or  pearly  scales.  Most  of  the  oleic  amides  and  linolenic 
anilides  are  oils. 

*  German  Patent  No.  275,344,  June  15,  1911. 

fSeifen.  Ztg.,  1914,  442. 

t  Univ.  Naples,  Gazz.,  chim.  ital.,  1917,  47.  I,  93;  Chem.  Aba.,  1918,  1172. 


METHODS  OF  HYDROGENATION  85 

Hydrazine  hydrate  has  been  found  by  Falciola  and  Mannino  * 
to  react  with  fats,  forming  solid  products. 

When  hydrazine  hydrate  (90  or  50  per  cent  solution)  is  added  to  olive  oil, 
a  turbidity  is  produced  which  separates  after  a  few  hours  as  a  more  or  less 
concrete  mass,  depending  on  the  amount  of  hydrazine  used;  the  action  takes 
place  in  the  cold  without  appreciable  development  of  heat  and  with  slight 
ammoniacal  odor,  which  soon  disappears.  The  greater  part  of  the  white  solid 
substance  thus  produced  dissolves  in  warm  alcohol,  from  which  it  crystallizes 
on  cooling.  The  solidifying  point  is  about  105°  C.  Other  oils  behave  similarly. 
Triolein  treated  with  excess  of  90  per  cent  hydrazine  hydrate  rapidly  whitens 
and  hardens.  Tristearin  gives  a  similar  product,  m.p.,  112°  to  114°,  and  tripalmitin 
yields  a  body  of  m.p.  108°  to  109°. 

ELAIDIN 

Many  years  ago  considerable  attention  was  paid  to  the  production  of  hardened 
fats  by  the  transformation  of  olein  into  elaidin.  Among  these  proposals  are  those 
represented  by  British  Patents  as  follows: 

Name.  Patent  Number.       Date. 

Cambaccrts 1806  1860 

Bryant 2675  1860 

de  Bassano 1099  1861 

Tolhausen 2127  1861 

de  Bassano  and  Brudenne 2726  1861 

La  Peyrouse 1385  1862 

Barnes 817  1863 

Morgan-Brown 3021  1874 

See  also  U.  S.  Patent  to  McCarty,  No.  292,669  dated  January  29,  1884. 

The  effect  of  pressure  and  .temperature  on  hydrogenation  is  dis- 
cussed by  Brochet  f  who  does  not  regard  a  high  pressure  of  hydrogen 
to  be  necessary  in  most  hydrogenating  operations,  although  in  prac- 
tice the  employment  of  pressure  may  be  useful. 

In  all  cases  a  much  lower  temperature  may  be  employed  than  that  adopted 
in  the  method  of  Sabatier  and  Senderens.  The  proportion  of  nickel  (obtained 
by  reduction  of  the  oxide  at  about  300°  C.)  may  be  as  low  as  0.1  to  0.5  per 
cent  of  the  weight  of  liquid  in  some  cases.  The  method  is  applicable  to  the 
hydrogenation  or  reduction  of  various  organic  compounds.  A  mixture  of  the 
active  metal  and  the  liquid  (the  substance  to  be  treated,  or  its  solution  or  sus- 
pension in  a  suitable  liquid)  is  agitated  vigorously  in  presence  of  hydrogen  at 
ordinary  or  higher  pressures.  - 

Referring  to  the  hydrogenation  of  fatty  oils  by  contacting  the  oil  and  catalyzer 
with  hydrogen,  Brochet  states  that  it  was  not  foreseen  that  this  process  might 
be  applicable  to  products  other  than  fatty  bodies,  as,  generally  speaking,  it  was 
believed  that  the  moistening  of  the  catalytic  metal  completely  checked  the 
reaction,  J 

*  Ann.  chim.  applicata  2,  351-6,  1914;   Chem.  Abs.,  1915,  866. 
fCompt.  rend.,  1914,  158,  1352. 
j  British  Patent  No.   16,936,  1913. 


86  THE  HYDROGENATION  OF  OILS 

The  method  is  stated  to  present  the  following  advantages: 

1.  It  permits  of  the  utilization  of  the  hydrogen  at  a  temperature  which  may 
be   much    lower   than  the  boiling-point  of  the  product  treated,  which  affords  the 
advantage  that,  on  the  one  hand,  products  non-volatile  at  the  reaction  temperature 
can  be  employed,  while  on  the  other  hand  hydrogenation  can  be  effected  at  a 
relatively  low  temperature.     It  is  therefore  possible,  Brochet  declares,  to  obtain 
products   that   have   never  hitherto  been   obtained  and   to   avoid   the  formation 
of  undesirable  products,  and,  by  suitably  selecting  the  temperature  for  the  op- 
eration, it  is  also  possible  to  obtain  the  desired  body  in  a  state  of  gre  t  purity. 
With  phenol  and  nitrobenzene,  the  hydrogenation  in  the  first  and  the  reduction 
in  the  second  place  take  place  below  100°. 

2.  Products  infusible  at  the  reaction  temperature  but  soluble  either  in  water 
or  in  an  appropriate  liquid,  such  as  ethyl  alcohol,  amyl    alcohol,    cyclohexanol, 
glycerine,  and  so  forth,  or  insoluble  products  maintained  in  suspension  in  a  vehicle 
can  be  hydrogenated. 

EXAMPLE  1.  One  per  cent  of  reduced  nickel  (obtained  from  oxide,  carbonate, 
etc.)  is  added  to  the  phenol.  It  is  placed  in  an  apparatus  heated  to  approx- 
imately 100°  to  120°  C.,  and  subjected  to  the  action  of  hydrogen  acting  at  a 
pressure  of  from  10  to  15  kilogrammes  per  square  centimetre.  Agitation  is 
effected  in  such  a  manner  as  frequently  to  renew  the  contacts  between  the  gas 
and  the  metal  impregnated  with  phenol.  The  hydrogen  is  rapidly  absorbed; 
if  the  supply  of  hydrogen  is  cut  off,  the  apparatus  having  previously  been 
exhausted  of  air,  it  is  found  that  a  vacuum  forms  in  the  apparatus.  In  this 
manner  the  phenol  is  transformed  into  cyclohexanol  and  by  reason  of  the  low 
reaction  temperature,  neither  the  formation  of  cyclohexane  nor  of  cyclohexanone 
is  observed.  The  filtered  liquid  is  subjected  to  distillation  and  the  catalyzer 
is  utilized  for  a  fresh  operation. 

EXAMPLE  2.  One  kilo  of  paranitraniline  is  dissolved  in  a  kilo  of  amyl  alcohol 
and  1  per  cent  of  reduced  nickel  is  added.  The  mixture  is  subjected  to  the 
action  of  hydrogen  at  120°  to  130°  C.,  and  at  a  pressure  of  10  to  15  kilogrammes 
per  square  centimetre  and  agitated  continuously.  The  reaction  is  very  rapid 
and  the  catalyzer  is  separated  by  filtration,  and  the  paraphenylene  diamine  crys- 
tallized by  cooling. 

In  these  two  examples  the  absorption  of  the  hydrogen  is  theoretical,  so  that 
the  end  of  the  reaction  is  noticeable  by  cessation  of  absorption. 

Brochet  and  Bauer  *  have  hydrogenated  a  number  of  aromatic  compounds 
containing  an  ethylenic  linkage  in  the  side  chain  i.nd  one  aliphatic  compound. 
1.  Octene  readily  yields  octane.  Cinnamic  acid,  its  sodium  salt,  and  its  methyl 
ester  yield  phenylpropionic  acid  and  its  corresponding  derivatives.  The  hydro- 
genation proceeds  better  with  the  sodium  salt  than  with  the  free  acid,  1 
the  conversion  readily  takes  place  on  using  the  sodium  salt.  Ane thole,  eugenol 
and  safrole  readily  undergo  hydrogenation  at  60°  to  80°  C.,  while  for  isoeugenol 
ordinary  temperature  suffices.  Brochet  and  Cabaret  f  find  that  the  substances 
containing  aliphatic  ethylenic  linkage  which  were  hydrogenated  in  the  presence 
of  active  nickel  under  a  slightly  increased  pressure  by  Brochet  and  Bauer  also 
undergo  hydrogenation  under  atmospheric  pressure,  but  in  this  case  the  reac- 
tion takes  place  far  more  slowly  and  requires  a  larger  amount  of  the  catalyst. 

*  Comptes  rend.,  1914,  159.  190. 
.,  326. 


METHODS  OF  HYDROGENATION  87 

Brochet  *  suggests  a  further  modification  by  the  substitution  of  vigorous  shaking 
for  the  high  pressure,  10  to  15  kilos  per  square  centimetre,  first  recommended. 
This  method  is  applicable  generally  to  compounds  containing  acetylenic  or  ethyl- 
enic  bonds  and  to  some  easily  reducible  substances  such  as  indigo.  Details 
are  given  for  the  reduction  of  sodium  cinnamate  to  phenyl-propionate,  using 
reduced  nickel  as  the  catalyzer  and  hydrogen,  and  for  the  preparation  of  indigo- 
white  by  reduction  of  indigo  both  by  hydrogen  and  by  water  gas. 

In  a  paper  on  polymerized  drying  oils,  Morrill  f  states  that  linseed 
oil  from  various  sources  was  thickened  in  bulk  or  in  smaller  quantities 
in  the  laboratory,  and  to  avoid  oxidation  the  operation  was  performed 
as  far  as  possible  in  an  atmosphere  of  carbon  dioxide  or  hydrogen. 

Hydrogen  under  ordinary  conditions  or  under  pressure  without  a  catalyst  is 
stated  to  have  no  action  on  unsaturated  fatty  acids;  I  nevertheless,  it  was 
found  that  under  the  conditions  of  the  experiments  a  very  slight  addition 
occurred  and  subsequently  carbon  dioxide  was  used  instead.  The  oil  was  heated 
for  twenty-eight  to  sixty  hours  at  260°  C.,  and  the  thickened  oil  was  completely 
soluble  in  light  petroleum. 

While  Shuck  §  was  carrying  on  some  experiments  on  the  catalytic 
hydrogenation  of  naphtha-extracted  corn-oil,  he  observed  that  a  sample 
which  had  not  been  purified  sufficiently  to  allow  the  catalyzer  to  act 
and  which  had  not  hardened,  nevertheless  was  rendered  odorless  and 
palatable  by  the  action  of  the  hydrogen  on  the  oil  containing  a  catalyzer 
in  suspension.  Although  no  appreciable  hardening  had  taken  place, 
the  improvement  in  odor  and  taste  was  so  marked  that  a  fresh  sample 
was  treated  under  identical  conditions  except  that  no  catalyzer  was 
present.  This  sample  proved  to  be  equal  in  odor  and  taste  to  that 
treated  with  hydrogen  in  the  presence  of  a  catalyzer  and  thus  showed 
that  the  catalyzer  did  not  function  in  the  removal  of  odor  from  the 
corn  oil.  Fish  oil  also  was  deodorized. 

The  method  of  deodorizing  any  oil  or  fat  by  this  process  consists  of  blowing 
hydrogen,  or  a  gas  whose  principal  constituent  is  hydrogen,  through  the  heated  oil 
and  allowing  the  hydrogen  with  the  entrained  vapors  from  the  oil  to  escape  freely 
from  the  containing  vessel  until  the  desired  result  is  obtained.  In  the  commercial 
application  of  this  process,  the  fatty  acid  and  other  fumes  are  condensed  and  washed 
from  the  hydrogen  which  is  thus  completely  purified  and  used  over  again.  The 
entire  apparatus  should,  of  course,  be  filled  with  hydrogen  to  the  exclusion  of  all 
oxygen  from  the  air  at  the  time  of  its  first  use.  Thereafter  each  new  batch  of  oil  is 
introduced  and  the  deodorized  oil  withdrawn  through  pipes  so  that  no  air  enters 

*  J.  S.  C.  I.,  1915,  1116.    Second  Addition  dated  Nov.  19,  1913,  to  French  Patent  No. 
458,033,  July  27,  1912;  J.  S.  C.  I.,  1913,  1031  and  1914,  18. 
fJ.  S.  C.  I.,  1915,  105. 

t  Thorpe's  Dictionary,  Oils,  Fats  and  Waxes,  2d  Ed.,  Vol.  3,  57. 
§  Met.  &  Chem.  Eng.,  1916,  608. 


88  THE  HYDROGENATION   OF  OILS 

the  apparatus.  A  means  of  drying  the  hydrogen  is  provided  in  the  gas-purifying 
system  if  the  oil  being  treated  contains  appreciable  quantities  of  water. 

Cocoanut  oil  was  treated  by  this  process  at  the  same  time  that  some  of  the  same 
oil  was  deodorized  with  superheated  steam.  Both  samples  were  put  in  clean  tins 
with  lids  loosely  laid  on,  then  alternately  kept  in  a  warm  place  where  the  oil  was 
liquid  during  the  day  and  in  a  cool  place  at  night  for  four  months.  The  steam- 
deodorized  oil  became  rancid  in  a  few  weeks  and  was  very  poor  in  quality  in  two 
months.  The  hydrogen-deodorized  oil  was  pleasant  to  taste  after  two  months' 
storage. 

Among  the  commercial  possibilities  of  this  process  Shuck  states  that  the  purifying 
of  fish  oils  so  as  to  render  them  edible  is  of  prime  importance.  Even  the  deodoriza- 
tion  of  fish  oils  for  technical  purposes  is  a  matter  of  interest. 

While  not  taking  the  place  of  catalytic  hydrogenation  of  fish  oils  because  the  oil 
is  not  hardened,  Schuck  considers  the  process  very  much  cheaper  to  operate.  It  is 
claimed  that  fish  stearine  which  is  naturally  a  solid  fat  at  ordinary  temperatures 
can  be  made  into  an  acceptable  cooking  fat  at  very  low  cost  by  this  process. 
Fats  which  have  been  burnt  from  continued  use  in  cooking  and  have  absorbed 
the  odor  of  fish,  onions,  garlic,  etc.,  can  be  rendered  perfectly  bland  and  neutral 
by  this  deodorizing  process.  Likewise  garbage  grease  and  rendering-works  fats 
can  be  purified  and  freed  from  objectionable  odor.  This  latter  class  of  fats 
usually  contains  substances  that  "  poison  "  a  catalyzer  and  therefore  are  not 
easily  deodorized  by  catalytic  hydrogenation.  Medicinal  castor  oil,  it  is  claimed, 
can  be  rendered  entirely  free  from  its  characteristic  odor  and  taste  while  still 
•  ^  retaining  its  medicinal  properties.  A  temperature  of  185°  C  may  be  used. 

Certain  vegetable  oils  such  as  soya  bean  oil,  not  readily  deodorized  with  steam, 
Shuck  asserts  are  rendered  bland  and  palatable  by  this  process.* 

Schrauth  f  observes  that  Varrentrapp's  reaction  is  applicable  to 
all  unsaturated  fatty  acids,  which  in  this  way  may  be  converted 
into  saturated  fatty  acids  containing  a  smaller  number  of  carbon  atoms. 
For  example,  clupanodonic  acid,  which  is  the  cause  of  the  charac- 
teristic odor  of  marine  animal  oils,  is  slowly  transformed  into  satu- 
rated fatty  acids  and  it  is  possible  in  this  way  to  obtain  up  to  85  per 
cent  of  a  perfectly  white  solid  distillate  from  the  mixed  fatty  acids 
of  the  oils,  provided  that  glycerol  is  absent.  Marine  animal  oils 
of  the  best  quality  yield  tallow-like  fats,  which  when  mixed  with 
other  fats  give  good  lathering  soaps,  while  the  fatty  acids  from  refuse 
marine  animal  oils  yield  products  which  resemble  the  fatty  acids  of 
palmnut  and  cocoanut  oils  both  in  properties  and  composition. 

The  electrolytic  reduction  of  organic  bodies  and  especially  fatty 
acids  or  esters  is  carried  out  by  Higgins  |  with  the  aid  of  nickel  or 
cobalt  oxide  or  hydroxide. 

*  See  also  U.  S.  Patent  No.  1,260,072,  March  19,  1918. 

t  Seifenfabr.,  1915,  35,  877-879.  Z.  angew.  Chem.,  1916,  29,  Ref.,  31;  J.  S.  C.  I., 
1916,  428. 

JJ.  S.  C.  I.,  1911,  982;  British  Patent  No.   18,969,  1910. 


METHODS  OF  HYDROGENATION  89 

The  catalyzing  agent  may  constitute  the  whole  or  part  of  the  electrode  from 
which  hydrogen  is  normally  disengaged,  or  may  be  in  suspension  in  the  elec- 
trolyte composed  of  or  containing  the  body  to  be  reduced.  According  to  one 
mode  there  is  formed  a  coherent  mass  composed  of  the  oxide  or  hydroxide  of 
cobalt  or  nickel,  or  a  mixture  of  these,  and  a  suitable,  chemically  inert,  binding 
material,  this  coehrent  mass  constituting  the  cathode.  For  instance  the  oxide 
or  hydroxide  of  cobalt,  or  nickel,  is  mixed  with  or  deposited  upon  kieselguhr, 
pumice,  or  other  porous  inert  powder,  and  the  whole  formed,  with  or  without 
the  addition  of  cement,  or  gums,  into  a  coherent  mass  by  mechanical  pressure; 
or  the  catalytic  material  may  be  mixed  with  a  cane  sugar  solution  which,  on 
subsequent  roasting  in  a  non-oxidizing  atmosphere,  yields  a  porous  mass  of 
carbon-containing  the  active  ingredients.  Higgins  also  states  that  perforated 
plates  such  as  are  commonly  used  in  secondary  cells  may  be  employed  to  sup- 
port the  catalyzing  agent  either  alone  or  mixed  with  the  binding  material  re- 
ferred to  above. 

A  survey  and  discussion  of  the  field  of  hydrogenation  by  vanLeent* 
involves  a  comparison  of  the  physical  and  chemical  properties  of 
cottonseed,  linseed  and  whale  oils  before  and  after  hydrogenation. 
Methods  for  the  detection  and  determination  of  nickel  in  the  products 
are  discussed.  Hydrogenation  with  and  without  high  pressures  showed 
that  olive  and  peanut  oils  are  especially  adapted  to  hardening  at 
atmospheric  pressure.  Linseed  oil  is  stated  to  hydrogenate  but  very 
little  even  with  platinum  black  as  catalyst. 

The  hydration  of '  unsaturated  organic  acids  is  carried  out  by 
Schicht  A.  G.  and  Griin  f  by  heating  salts  of  the  acids  with  water 
in  the  presence  of  small  amounts  of  an  alkali  substance,  under  pres- 
sure, whereby  water  is  added  directly.  The  double  union  disappears — 
the  iodine  number  decreases  continuously  and  hydroxyl  and  ether  groups 
are  formed.  E.g.,  500  g.  linoleic  acid  (iodine  number,  174.0)  were 
slightly  more  than  neutralized  with  40°  NaOH,  and  heated  in  a 
pressure  vessel  for  three  hours  to  270°  to  280°.  The  viscous  liquid 
reaction  product  showed  an  iodine  number  of  83.8. 

SYNTHETIC  ESTERS  OF  OLEIC  AND  OTHER  FATTY  ACID  AND  THEIR 
HYDROGENATED  PRODUCTS 

In  1906  Bedford  t  studied  the  esterification  of  linolic  and  linolenic 
acid  and  the  hydrogenation  of  these  esters  in  the  presence  of  finely- 
divided  nickel.  The  ethyl  and  methyl  esters  of  these  acids  were  pre- 
pared by  him  as  follows : 

*Chem.  Weekblad   13,  712-55,   1916;    Chem.  Abs.,   1917,  218. 
t  German  Patent  No.  287,660,  July  16,  1914;    Chem.  Abs.,  1916,  2128. 
J  "  Uber  die  Ungesattigten  Saiiren  des  Leinols,"  Dissertation,  Erlangen,  1906;  Ber., 
42,  1909,  1324. 


90  THE  HYDROGENATION  OF  OILS 

The  free  fatty  acid  was  boiled  under  reflux  with  an  excess  of  the  alcohol 
in  the  presence  of  a  small  amount  of  sulphuric  acid.  The  product  was  then 
treated  with  an  excess  of  sodium  bicarbonate  solution.  The  oil  that  separated 
out  was  decanted  off  and  dissolved  in  ether.  The  ether  solution  was  washed 
with  water,  dried  with  anhydrous  sodium  sulphate  and  then  distilled  to  remove 
the  ether.  The  oil  left  behind  was  purified  by  vacuum  distillation.  The  ethyl 
esters  of  linolic  and  linolenic  acid  were  hydrogenated  in  the  presence  of  finely- 
divided  nickel  at  about  180°  C.  Ethyl  stearate  was  obtained  in  both  cases. 

Methyl  esters  derived  from  thickened  linseed  oil  were  hydrogen- 
ated by  Morrell  *  who  employed  colloidal  palladium  as  a  catalyzer. 
Stearic  acid  in  good  yield  was  obtained  from  the  products  of  hydro- 
genation. 

The  methyl,  ethyl,  propyl,  isobutyl,  amyl,  benzyl,  and  glyceryl  esters 
of  oleic  acid  were  prepared  in  the  author's  laboratory.!  They  were 
all  liquid  at  the  ordinary  temperature,  and  yielded  practically  satu- 
rated products  when  hydrogenated  in  the  liquid  state,  at  an  increased 
temperature,  in  presence  of  reduced  nickel.  The  nature  of  the  alcohol 
did  not  seem  to  have  much  effect  on  the  rate  or  degree  of  hydrogen- 
ation.  A  product  derived  by  heating  oleic  acid  and  aniline  was  found 
to  hydrogenate  readily  to  form  a  very  hard  product. 

Methyl  Oleate.  U.  S.  P.  oleic  acid  (56.4  g.)  was  dissolved  in  25.6  g.  acetone- 
free  methyl  alcohol.  The  solution  was  treated  with  0.7  g.  sulphuric  acid  and 
then  boiled  for  5}  hours.  The  product  had  an  acid  number  of  17.6.  After 
washing  with  alkali  the  acid  number  of  the  oil  fell  to  1.3.  The  iodine  number 
was  found  to  be  87.0.  The  theoretical  iodine  number  of  methyl  oleate  is  85.8. 

Hydrogenation  of  Methyl  Oleate.  A  portion  of  methyl  oleate  containing  1 
per  cent  of  finely-divided  metallic  nickel  (reduced  for  fifteen  to  twenty  minutes 
in  a  stream  of  hydrogen  at  320°  to  350°  C.)  was  treated  for  about  two  hours 
at  about  180°  to  200°  C.  with  hydrogen  which  was  simply  allowed  to  bubble 
through  the  liquid  as  a  brisk  stream,  thereby  maintaining  the  catalyzer  in  sus- 
pension. The  solid  product  obtained  after  filtration  was  white  and  crystalline. 
It  had  an  iodine  number  of  0.4  and  melted  at  37°  C. 

Ethyl  Oleate.  Ethyl  oleate  containing  1  per  cent  of  metallic  nickel  (reduced 
for  fifteen  minutes  in  a  stream  of  hydrogen  at  320°  to  350°  C.)  was  exposed 
to  a  rapid  current  of  hydrogen  for  about  two  hours.  The  oil  was  filtered  through 
an  ordinary  filter  paper  in  the  hot  oven.  The  product  melted  at  31°  C.  Its 
iodine  number  was  5.3. 

Propyl  Oleate.  The  hydrogenation  in  this  case  was  carried  out  under  con- 
ditions practically  identical  to  those  employed  in  the  hydrogenation  of  methyl 
and  ethyl  oleate.  The  hardened  oil  had  an  iodine  number  of  1.3.  It  melted 
at  27°  C. 

Iso-butyl  Oleate.  The  ester  was  hydrogenated  for  about  two  hours  in  the 
presence  of  1  per  cent  metallic  nickel  (reduced  for  fifteen  minutes  at  320°  to 
350°  C.).  The  temperature  of  hydrogenation  was  180°  to  200°  C.  The  hydro- 

*  J.  S.  C.  I.,  1915,  107. 

t  J.  Ind.  Eng.  Chem.,  1916,  1105;  J.  S.  C.  I.,  1917,  39;  Chem.  Abs.,  1917,  218.  See 
also  U.  S.  Patent  No.  1,277,708,  Sept.  3,  1918. 


METHODS   OF   HYDROGENATION 


91 


genated  product  was  soft  and  translucent  and  distinctly  crystalline.  It  somewhat 
resembles  crude  paraffine.  It  had  an  iodine  value  of  0.2  and  melted  at  25°  C. 

Amyl  Oleate.  This  ester  was  hydrogenated  under  conditions  similar  to  those 
employed  above.  The  hydrogenated  product  was  soft  and  non-homogeneous, 
consisting  of  a  liquid  oil  and  a  crystalline  body.  It  had  an  iodine  value  of  1.7 
and  melted  at  22°  C. 

Glycerine  Oleate.  Oleic  acid  (56.4  g.)  and  18.4  g.  glycerine  were  heated  for 
five  hours  at  240°  C.  with  continuous  stirring.  The  oily  product  was  washed 
several  times  with  warm  water  and  dried.  Its  acid  number  was  0.6.  In  cool 
weather  a  crystalline  body  formed  which  rendered  the  ester  opaque.  The  iodine 
number  of  the  product  was  69.4.  Pure  glycerol  mono-oleate  has  an  iodine 
number  of  71.3.  The  ester  was  hydrogenated  in  the  usual  way.  Treatment 
with  hydrogen  for  about  two  hours  at  180°  to  200°  C.  gave  a  product  which 
melted  at  59°  C.  and  possessed  an  iodine  number  of  6.5.  The  hydrogenated 
product  was  similar  in  appearance  to  a  good  grade  of  hardened  cottonseed  oil, 
except  that  it  was  somewhat  darker  in  color. 

Benzyl  Oleate.  Hydrogenation  in  the  presence  of  finely-divided  reduced  nickel 
gave  a  product  which  had  an  iodine  value  of  6.3  and  a  melting-point  of  28°  C. 

Oleic  Acid  and  Aniline.  Aniline  (24.4  g.)  and  37  g.  oleic  acid  were  heated 
under  a  reflux  condenser  for  four  hours  at  170°  to  190°  C.  The  mixture  darkened 
considerably.  It  was  steam-distilled  until  the  distillate  was  free  from  aniline. 
The  acid  number  of  the  steam-distilled  product  was  30.5.  It  became  solid  on 
standing.  The  substance  was  treated  with  a  solution  of  sodium  hydroxide  and 
washed  free  from  alkali  and  sodium  oleate.  The  acid  number  of  the  product 
was  reduced  to  3.6.  The  product  melted  at  34°  C.  It  was  dark  brown  in  color 
and  had  a  greasy  feel.  The  material  was  hydrogenated  for  two  hours  at  190° 
to  200°  C.  in  the  presence  of  1  per  cent  finely-divided  reduced  metallic  nickel. 
The  hydrogenated  product  was  filtered  in  the  hot  oven.  It  had  an  iodine  num- 
ber of  30.5.  The  iodine  value  of  the  unhydrogenated  substance  was  69.5.  The 
iodine  value  of  oleic  anilide  is  71.6.  The  product  melted  at  76°  C.  and  was 
very  hard  and  brittle. 

A  tabulation  of  these  results  follows. 


Ester. 

Acid  Number. 

Iodine  Value. 

HYDKOGENATJON  PBODUCT 

M.  pt.,  °  C. 

Iodine  Value. 

Methyl  oleate  

1.3 
0.6 
0.5 
0.4 
0.7 
0.7 
0.6 
3.6 

87.0 
83.3 
77.9 
75.7 
71.3 
62.3 
69.4 
69.5 

37 
31 
27 
25 
22 
28 
59 
76 

0.4 
5.3 
1.3 
0.2 
1.7 
6.3 
6.5 
30.5 

Ethyl  oleate  
Propyl  oleate   

Isobutyl  oleate 

Amyl  oleate  

Benzyl  oleate 

Glycerol  mono-oleate  .... 
(Aniline  compound)        .  . 

In  the  catalytic  hydrogenation  of  fatty  acids  and  their  glycerides, 
the  speed  of  reaction  is  maintained  constant  *  by  gradually  raising 

*  Soc.  de  Stearinerie  et  Savonnerie  de  Lyon  and  P.  Berthon.     British  Patent  No. 
107,969,  June  25,  1917. 


92  THE  HYDROGENATION  OF  OILS 

the  temperature  and  adding  additional  catalyst,  and  sudden  rises 
in  temperature  are  avoided  by  providing  a  heat-exchange  appara- 
ratus  for  the  hydrogen  entering  and  leaving  the  reaction  chamber. 
The  hydrogen  is  purified  and  dried  by  subjection  to  a  low 
temperature  and  free  fatty  acid  distilling  over  is  separated  from  the 
hydrogen.  In  an  example  soya  oil  is  treated  at  200°,  the  temper- 
ature gradually  raised  to  300°  and  the  catalyst  introduced  little  by 
little.  In  another  example  whale  oil  is  treated  at  170°;  the  reaction 
which  is  at  first  violent,  tends  to  become  quieter  and  is  then  revived 
by  adding  more  catalyst.  The  amount  of  free  acid  in  this  product 
does  not  exceed  0.5  per  cent. 

The  application  of  esterification  as  a  means  to  reduce  free  fatty 
acid  has  been  utilized  by  Dreymann  *  in  the  treatment  of  oils  which 
which  cannot  be  readily  refined  by  caustic  alkali. 

Dreymann  states  that  the  presence  of  even  as  small  a  quantity  as  2  per 
cent  of  free  fatty  acid  in  an  oil  is  sufficient  to  greatly  impair  the  effectiveness 
of  the  catalytic  agent  used  in  the  hydrogenation  process.  Hence  it  is  the  prac- 
tice to  first  carefully  neutralize  the  oil  by  means  of  caustic  soda.  If  the  amount 
of  the  free  fatty  acids  exceeds  5  per  cent,  their  removal  by  caustic  alkali 
refining  is  difficult  and  is  attended  with  considerable  loss  and  expense.  In  con- 
sequence, Dreymann  states  only  high-grade  neutral  oils  are  being  used  for  hydro- 
genation purposes.  Dreymann  proposes  to  meet  the  difficulty  by  esterifying  the 
free  fatty  acid  of  the  oil  with  alcohol,  which  he  states  can  be  hydrogenated  as 
readily  as  a  pure  glyceride.  In  this  way,  oils  and  fats  containing  as  much  as 
20  per  cent  of  free  fatty  acid  may  be  hardened.  Apply^ig  the  process  to  a 
fatty  oil  containing  about  20  per  cent  of  free  fatty  acid,  Dreymann  recommends 
the  use  of  5  to  8  parts  of  absolute  ethyl  alcohol  to  100  parts  of  the  oil.  A 
small  quantity  of  hydrochloric  acid  is  added  to  act  as  a  catalyzer  in  the  ester- 
ification operation  and  calcium  chloride  is  introduced  to  serve  as  a  dehydrating 
agent.  Dreymann  recommends  3  parts  of  hydrochloric  acid  and  20  parts  of 
calcium  chloride.  The  mixture  is  heated  to  a  temperature  of  about  90°  C., 
for  three  hours,  after  which  time  the  product  is  washed  with  water  and  will 
then  be  found  to  have  a  low  content  of  free  fatty  acid,  in  general,  less  than 
3  per  cent.  This  amount  of  free  fatty  acid  can  be  readily  removed  by  the 
caustic  soda  refining  process.  When  the  oil  or  fat  contains  30  per  cent  or  more 
of  free  acid,  Dreymann  states  it  is  advantageous  to  remove  the  glycerine  as 
for  example,  by  the  Twitchell  process.  The  fatty  acids  thus  obtained  can  be 
converted  into  esters  by  treatment  with  alcohol,  the  proportion  of  alcohol  in 
this  case  being  increased  to  20  parts.  He  states  that  the  esters  thus  produced 
contain  only  1  to  3  per  cent  free  fatty  acid,  which  may  be  removed  by  refining 
with  alkali.  The  application  of  the  process  to  the  treatment  of  inferior  products, 
such  as  cotton  oil,  soap  stock^  and  garbage  grease,  is  recommended. 

The  hydrogenation  of  fatty  material  containing  such  quantities  of 
free    fatty    acids    as    tend   to   interfere  seriously   with  the   catalytic 

*U.  S.  Patent  No.   1,228,888,  June  5,  1917. 


METHODS   OF   HYDROGENATION 


93 


process  is  carried  out  by  Ellis  *  by  esterifying  the  fatty  acids  with 
glycerin. 

This  may  be  carried  out  by  heating  the  oil  with  glycerin  to  a  temperature  between 
250°  and  285°  C.  for  two  or  three  hours.  The  reaction  mass  may  be  kept  out  of 
contact  with  air  by  introduction  of  a  current  of  hydrogen.  In  one  case  a  whale  oil 
having  an  acid  number  of  about  25  was  treated  with  5  per  cent  of  glycerin  and  the 
acid  number  was  reduced  to  approximately  1.  After  the  esterification  stage  has  been 
completed  a  catalytic  agent  is  added  to  the  oil  and  the  product  hydrogenated  at  a 
temperature  of  about  180°  C.  in  the  case  of  nickel  or  at  a  lower  temperature  if  a 
catalyzer  of  the  platinum  group  is  employed. 

An  apparatus  for  hydrogenating  oils  designed  by  Sugita  f  consists 
of  a  cylindrical  hydrogenating  vessel  or  converter  which  is  provided 
with  two  revolvable  shafts, 
one  within  the  other.  A 
propeller  with  a  number  of 
nozzles  for  supplying  hydro- 
gen, each  provided  with  an 
automatic  valve,  is  attached 
to  the  end  of  one  of  the 
shafts.  By  this  arrange- 
ment the  hydrogen  is 
made  to  contact  rapidly 
and  thoroughly  with  the  oil, 
thereby  facilitating  the  hy- 
drogenation. 

For  the  effective  mixing 
of  oil,  catalyzer  and  hy- 
drogen, Ittner  J  recommends 
an  apparatus  of  the  character 
shown  in  Fig.  4066. 

In  this  drawing  a  receptacle  containing  oil  is  equipped  with  a  peculiar  form  of 
agitating  and  hydrogen-mixing  device  shown  in  detail  in  Fig.  40cc.  The  latter  is 
termed  by  Ittner  a  centrifugal  distributor  or  injector.  It  is  set  below  the  normal 
level  of  the  oil  and  is  so  constructed  that  the  liquid  is  drawn  in  near  its  centre  and 
discharged  centrifugally  outward  so  that  circulation  of  the  iquid  is  effected.  The 
upper  part  of  the  chamber  is  filled  with  hydrogen  gas  which  may  be  at  atmospheric 
pressure  or  under  increased  or  decreased  pressure.  Th^  gas  is  drawn  through  the 
hollow  shaft  of  the  centrifugal  distributor  by  means  of  perforations  and  passes  out 
through  the  disc-shaped  portion  admixed  with  oil.  By  this  means,  Ittner  states, 
an  intermixture  of  the  liquid  and  gas  of  such  intimacy  is  obtained  that  ordinary 

*U.  S.  Patent  No.  1,261,911,  April  9,  1918.  See  also  No.  1,271,575  and  1,271,576, 
July  9,  1918. 

t  Japanese  Patent  No.  30,637,  January  19,  1917;   Chem.  Abs.,  1917,  2413. 
JU.  S.  Patent  No.  1,242,445,  October  9,  1917. 


FIG.  4066. 


94 


THE  HYDROGENATION  OF  OILS 


agitation  can  add  but  little  to  the  efficiency  of  the  operation.  In  fact,  he  states 
it  is  sometimes  advantageous  to  avoid  a  high  degree  of  agitation  of  the  liquid 
and  screens  or  baffles  may  be  so  placed  as  to  lessen  agitation. 


FIG.  40cc. 

A  method  of  automatic  regulation  of  the  supply  of  liquid  to  and  discharge 
of  liquid  and  removal  of  gas  from  pressure  vessels  for  mixing  liquid  with  gas  is 
described  by  Noll.* 

An  apparatus  for  bringing  liquids  and  gases  into  contact  with  each  other  which 
is  of  interest  to  the  hydrogenation  industry  is  described  by  Feld  f.  Fig.  4Qdd 
shows  a  simple  type  of  the  apparatus.  Gas  enters  the  stationary  bell,  a,  through 
the  pipe  e,  and  is  distributed  through  the  liquid,  g,  in  an  atomized  condition  by 
the  rotation  of  the  agitator,  d,  which  also  serves  to  agitate 
and  mix  the  liquid.  Over  twenty  modifications  of  the 
apparatus  are  shown. 

To  remove  traces  of  nickel  from  the  hardened 
product  obtained  by  hydrogenating  fatty  oils  with 
a  nickel  catalyzer,  WhitakerJ  recommends  treat- 
ment of  the  hardened  material  with  fuller's  earth. 
After  the  hydrogenated  fat  or  oil  leaves  the  hydro- 


FIG. 


genator  or  converter  or  after  it  has  passed  through  the  filter  press  and 
while  still  in  a  liquid  condition,  a  quantity  of  fuller's  earth  is  introduced. 
The  oil  agitated  is  therewith  and  the  earth  is  then  removed  by  filtration. 
Ordinarily  1  or  2  per  cent  by  weight  of  fuller's  earth  may  be  added, 
but  when  a  large  amount  of  nickel  soap  is  present  in  the  oil,  more 
than  this  quantity  of  the  earth  may  be  required.  Fuller's  earth, 
which  has  been  heated  to  100°  C.  is  stated  to  lose  its  efficiency  as  a 

*  German  Patent  No.  271,641,  May  9,  1913;    J.  S.  C.  I.,  1914,  469. 
tZeitsch.    angew.    Chem.,    Aufsatzteil,    1914,    224;     U.    S.    Patent    No.    1,110,914, 
September  15,  1914. 

JU.  S.  Patent  No.  1,242,624,  October  9,  1917. 


METHODS   OF   HYDROGENATION  95 

means  of  removing  traces  of  nickel,  so  that  care  should  be  taken  not 
to  operate  at  a  temperature  at  or  above  the  point  where  dehydration 
would  impair  its  usefulness. 

A  process  of  effecting  catalytic  reactions  is  described  by  Hagemann 
and  Baskerville,*  according  to  which  nickel  or  an  alloy  of  nickel  with 
a  small  amount  of  cobalt,  having  all  or  a  part  of  its  surface  oxidized, 
is  used  as  the  catalytic  body. 

Instead  of  using  the  material  in  the  form  of  leaves f  the  catalytic  agent  may 
be  used  in  the  form  of  wire  or  sheets  and  the  like,  having  a  very  slight  surface 
oxidation.  It  is  stated  that  alloys  of  nickel  with  a  small  amount  of  cobalt 
when  oxidized  on  the  surface  act  much  more  vigorously  as  catalyzers  cha^i 
either  pure  nickel  or  cobalt.  In  preparing  the  sheets,  wire,  or  other  suitable 
shapes  for  catalytic  use,  the  superficial  oxidation  is  carried  out  by  heating  in  air, 
oxygen,  or  ozone,  until  the  metal  surface  Ceases  to  be  bright.  The  revivification 
of  the  catalyzer  may  be  carried  out  by  first  removing  any  fatty  material  or  other 
foreign  accumulations  from  the  sheets  or  wires  by  extraction  with  a  solvent. 
The  nickel  basis  is  then  dried  and  heated  in  an  oxidizing  atmosphere  to  a  tem- 
perature of  300°  C.  or  higher  until  oxidation  has  gone  on  to  slight  depth, 
after  which  the  catalyzer  is  subjected  to  the  action  of  a  reducing  gas,  such  as 
hydrogen,  at  a  temperature  of  300°  C.  to  reduce  the  nickel  oxide  formed,  then 
the  material  is  subjected  to  the  action  of  air  at  about  300°  C.  for  some  time, 
until  the  surface  becomes  coated  to  a  greater  or  less  extent  with  a  thin  film  of  oxide. 

The  baffle-plate  principle  is  applied  to  the  hydrogenation  of  oils 
by  Maxted  and  Ridsdale,{  who  obtain  a  large  reacting  surface  of 
unsaturated  oil  and  hydrogen-  by  projecting  the  mixture  through 
a  vertical  column  provided  with  fixed  horizontal  propeller-like  baffle 
plates  so  shaped  and  placed  in  opposition  to  each  other  that  the  moving 
liquid-gas  mixture  is  rotated  alternately  clockwise  and  anti-clockwise. 

According  to  Higgins,§  an  effective  apparatus  for  hydrogenation 
is  secured  by  the  employment  of  agitators  equipped  with  gas  cups 
as  shown  in  Fig.  4Qee. 

Beaters  or  vanes  are  employed  with  a  number  of  conical  cups  closed  at  their 
bases  and  open  at  their  narrower  ends  where  they  are  mounted  upon  the  plate 
forming  the  beater  or  vane.  The  plate  is  provided  with  a  hole  of  corresponding 
size  and  the  cup  is  mounted  on  the  plate  so  that  the  opening  in  the  cup  is 
coincident  with  the  hole  in  the  plate.  Such  conical  cups  are  uniformly  dis- 
tributed and  are  mounted  upon  one  side  of  the  beaters  or  vanes.  Between  he 
respect'. ve  cups,  holes  are  formed  in  the  plate.  These  holes  are  advantageously 
arranged  all  over  the  plate  so  as  to  form  continuous  longitudinal  and  trans- 
verse rows  intermediate  the  respective  rows  of  conical  cups.  By  such  means, 

*  U.  S.  Patent  No.  1,238,137,  August  28,  1917. 
tU.  S.  Patent  No.  1,083,930,  January  13,  1914. 

t  British  Patent  No.  109,993,  September  29,  1916;    J.  S.  C.  I.,  1917,  1185. 
§U.   S.   Patent  No.   1,170,815,  February  8,   1916;    Chem.  Abs.,   1915,  4;    British 
Patent  No.  15,063,  June  30,  1913.     See  also  Schwarcman,  U.  S.  Patent  1,280,315. 


THE  HYDROGENATION  OF  OILS 


on  the  rotat  on  of  the  beaters  or  vanes,  the  cups  pass  into  the  liquid,  open  end 
fi  s  .  A  quant  ty  of  the  gas  thus  becomes  impri  c  ned  in  the  cups  and  as  the 
beater  or  vane  rotates  the  oil  passes  into  the  cup  and  the  gas  passes  out.  The 
gas  continues  to  pass  out  throughout  the  course  of  the  beater  or  vane  through 

the  liquid.  By  the  provision  of  holes 
intermediate  of  the  cups,  the  rush  of 
the  oil  through  these  holes  carries  the 
bubbles  of  gas  with  it,  and  thus  the 
gas  is  brought  into  intimate  contact 
with  the  liquid. 

The  hydrogenation  of  various 
resins  such  as  ordinary  rosin, 
damar,  sandarac,  shellac,  copal, 
pontianak,  is  described  by  Ellis.* 
Nickel,  copper,  cobalt,  palla- 
dium, or  platinum  may  be  used 
as  catalyzers.  The  resin  may 
be  hydrogenated  in  a  melted 
condition  or  in  solution  in  an 
inert  solvent.  Petroleum  or 
aromatic  hydrocarbons  may  be 
used  as  the  solvent  material.  A 
temperature  of  180°  C.  is  speci- 
fied and  a  pressure  of  hydrogen 
of  10  Ib.  or  more. 


FIG.  40  ee. 


TABLE  SHOWING  THE  COMPOSITION  OF  CERTAIN  OILS  AND  FATS 

(MOORE,   RlCHTER  AND  VAN  ARSDEL,) 


IODINE  NUMBER. 

CALCULATED  PERCENTAGES. 

No. 

Material. 

Original 
Material. 

Liquid 
Fatty  Acid. 

Saturated 
Glycerides. 

Olcin. 

Linolin. 

1 

Cottonseed  oil  

110.7 

149.5 

22.6 

26.9 

50.5 

2 

Cottonssed  stearine  

86.0 

149.8 

40.0 

20.5 

39.5 

1 

Peanut  oil. 

98  0 

121.7 

15.85 

54.9 

29.25 

4 

Corn  oil  

110.6 

133.0 

13.0 

46.0 

41.0 

5 

Olive  oil                         .    .  . 

82.0 

97.8 

12.4 

80.1 

7.5 

6 

Leaf  lard 

63  5 

105.3 

37.0 

52.4 

10.6 

7 

Compound  lard  

97.0 

143.0 

29.3 

29.1 

41.6 

8 

A  semi-solid  hydrogenated 

cottonseed  oil  

63.0 

101.0 

34.75 

57.2 

8.05 

A  thorough  study  of  the  results  of  partial  hydrogenation  of  cot- 
tonseed oil  has  been  made   by  Moore,  Richter,  and    Van  Arsdel.f 

*  U.  S.  Patent  No.  1,249,050,  December  4,  1917.       t  J-  Ind.  Eng.  Chem.,  1917,  451. 


METHODS   OF  HYDROGENATION  9> 

They  state  that  investigations  heretofore  have  considered  the  unsatu- 
rated  components  as  a  whole,  rather  than  as  individual  units  and 
that  they  have  studied  the  physical  and  chemical  changes  which  take 
place  in  oil  during  the  process  of  hydrogenation,  particularly  changes 
in  the  amount  and  character  of  the  various  fatty  glycerides,  and  the 
effect  of  variable  factors,  such  as  temperature  and  pressure. 

I.  HYDROGENATJON  CURVES 

For  the  ziudy  o  the  ;  lyceride  changes  during  hydrogenation,  (he  tests 
made  on  samples  'ncluded  iodine  number  and  iodine  number  of  liquid  fatty 
acids,  calculation  giving  the  "  component  glycerides  "  (olein,  linolin  and  satur- 
ated glycerides)  of  each  sample.  The  smooth  curves  drawn  through  the  points 
p'otted  on  triangular  diagrams  always,  in  the  cases  studied,  had  the  same  gen- 
eral shape,  suggestive  of  the  hyperbola,  concave  toward  the  right-hand  side  of 
the  triangle.  The  linolin  is  always  found  to  decrease  from  that  present  in  the 
original  oil  and  the  saturated  glycerides  always  increase,  while  the  olein  rises  to 
a  maximum  and  then  falls  continuously.  These  changes  are  what  would  be 
expected,  since  hydrogenation  must  cause  linolin  to  disappear,  forming  olein, 
while  olein,  hydrogenating  more  slowly,  would  at  first  increase  and  then  eventu- 
ally disappear,  forming  stearin,  a  saturated  glyceride.  The  shape  of  the  curve 
depends  upon  the  relative  velocity  of  these  two  actions,  and  it  appears  that  this 
relative  velocity  must  be  subject  to  important  variation,  according  to  the  experi- 
mental conditions. 

Effect  of  Temperature.  The  result  obtained  in  Fig.  40//  may  be  interpreted 
as  follows:  while  both  linolin  and  .olein  were  hydrogenated  faster  at  the  high 
temperature  than  at  the  low  temperature,  relatively  linolin  was  hydrogenated 
much  faster  at  the  high  temperature,  so  that  the  olein  had  a  greater  tendency 
to  accumulate  under  the  latter  conditions.  In  other  words,  both  unsaturated 
radi3als  are  acted  upon  in  both  cases,  but  at  the  higher  temperature  the  more 
highly  unsaturated  one  comes  nearer  to  being  singled  out  for  hydrogenation  thsn 
at  the  lower  temperature — the  action  is  more  "  selective."  This  would  be  the 
case  if,  for  instance,  the  temperature  coefficient  of  the  reaction  linolin-olein  is 
greater  than  that  of  the  reaction  olein-stearin,  but  in  view  of  the  complicated 
nature  of  the  glycerides  which  are  actually  present  that  explanation  is  doubtless 
too  superficial  to  be  the  entire  truth. 

ECect  of  Pressure.  The  influence  of  the  hydrogen  pressure  upon  the  course 
of  the  hydrogenation  may  be  illustrated  by  Runs  C  and  D  (Fig.  4000). 

Increasing  the  pressure  is  here  seen  to  have  the  opposite  effect  to  increasing 
the  temperature,  so  that  at  a  high  pressure  the  action  is  less  "  selective  "  than 
at  a  low  pressure.  An  obvious  corollary  of  this  conclusion  is  that  it  would 
appear  to  be  possible  to  duplicate  at  high  pressure  and  high  temperature  a  curve 
obtained  at  low  pressure  and  low  temperature,  while  the  reaction  as  a  whole 
might  be  made  to  proceed  many  times  as  fast  in  the  former  experiment  as  in 
the  latter. 

In  this  case  again  a  tentative  "  mechanism  "  may  be  put  forward.  It  should 
first  be  noted  that  the  occasional  hydrogenation  of  a  linolin  chain  clear  to  stearin 
instead  of  only  to  olein  would  have  the  same  apparent  effect  as  would  an  increase 
in  the  relative  velocity  of  the  olein-stearin  reaction.  Now  if  an  increase  IP 


THE  HYDROGENATION  OF  OILS 


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METHODS   OF  HYDROGENATION 


99 


hydrogen  concentration  at  the  catalyzing  surface  (such  as  would  be  produced 
by  increased  pressure)  caused  an  increase  in  the  number  of  linolin  chains  to 
which  four  atoms  of  hydrogen  were  added  at  once,  the  observed  effect  would 

follow. 

Influence  of  Percentage  of  Catalyzer.  The  influence  of  percentage  of  catalyzer 
was  illustrated  in  Experiments  C  and  E  (Fig.  40M).  In  this  case  the  observed 
result,  which  shows  a  divergence  in  the  same  direction  for  increased  percentage 
of  catalyzer  as  for  increased  pressure,  seems  to  be  at  variance  with  what  is 
commonly  understood  to  be  a  law  of  catalytic  reactions,  namely  that  if  the 
amount  (or  surface)  of  the  catalyzer  be  increased,  all  of  the  reactions  involved 
will  be  speeded  up  by  exactly  proportional  amounts.  In  this  case,  one  reaction 
(olein-stearin)  appears  to  be  accelerated  more  than  the  other.  The  scheme 
advanced  in  the  preceding  section  may  be  made  to  give  a  satisfactory  explana- 
tion; in  that  section  the  concentration  of  hydrogen  at  the  catalyzing  surface 


20     30      -10     50     60     70 
f'crceot  Saturated  Glyteridc 


FIG.  40f.— Runs  A  &  B.      FIG.  4(%.— Runs  C  &  D.      FIG.  40M.— Runs  C  &  E. 


was  taken  to  be  the  controlling  factor.  Now  increasing  the  percentage  of  cata- 
lyzer must  increase  this  concentration,  for  the  average  distance  between  a  cata- 
lyzer particle  and  the  hydrogen  bubble- surf  aces  is  made  smaller,  thereby  decreas- 
ing the  lag  between  the  "  demand  "  for  hydrogen  at  the  catalyzer  surface,  and 
the  "  supply/'  which  must  be  kept  up  by  the  processes  of  solution  and  diffusion. 
Thus  an  increase  in  percentage  of  catalyzer  would  cause  an  increase  in  the  forma- 
tion of  stearin  relative  to  the  change  in  linolin,  as  in  the  two  curves  reproduced 
above. 

Effect  of  Agitation.  The  influence  of  degree  of  agitation  on  the  path  of 
hydrogenation  was  dete  rmined  first  by  comparing  Experiments  C  and  F  (Fig.  40n), 
in  which  an  iron  apparatus  with  mechanical  agitator  was  used.  "  Degree  of 
Agitation  "  is  a  magni  tude  which  is  not  easily  expressed  in  quantitative  form, 
but  the  r.p.m.  of  an  agitating  device  may  serve  as  an  index  of  the  agitation, 
as  least  for  moderate  speeds. 

Another  pair  of  experiments  carried  out  in  the  glass  flask,  bubbling  hydrogen, 
conditions  were  identical  in  both  experiments  except  that  in  Run  H,  the  hydro- 
gen was  bubbled  through  the  flask  at  approximately  twice  the  rate  used  in 
Run  G  (Fig.  40jj). 

In  both  pairs  of  experiments  the  influence  of  increased  agitat'on  is  shown  to 
be  the  same  as  that  of  increased  pressure  or  per  cent  catalyzer,  and  in  the  case 
of  Runs  G  and  H  the  variation  in  the  curves  is  striking.  The  effect  of  doubling 
the  volume  of  gas  supplied,  when  the  bubbling  is  already  vigorous,  may  well  be 


100 


THE  HYDROGENATION  OF  OILS 


to  increase  the  true  "  agitation "  many  times.  On  the  other  hand,  doubling 
the  r.p.m.  of  a  mechanical  agitator  possibly  does  not  even  double  the  agita- 
tion, since  at  high  speeds  there  is  a  strong  tendency  for  the  whole  body  of  oil 
to  rotate  without  much  disturbance. 

It  may  readily  be  seen  that  the  "  mechanism  "  suggested  in  the  preceding 
section  applies  to  the  present  case  just  as  well,  since  the  effect  of  increasing 
the  agitation  is  to  increase  the  number  and  surface  of  hydrogen  bubbles  and  also 
to  decrease  their  average  distance  from  catalyzer  particles. 

Size  of  Apparatus.  The  size  of  the  apparatus  in  which  the  hydrogenation  is 
carried  out  apparently  does  not  affect  the  path  of  the  hydrogenation  as  appears 
from  the  data  of  Runs  7  and  J  (Fig.  40/c/c).  It  is  of  course,  not  certain  that  135 
r.p.m.  produces  the  same  "  degree  of  agitation  "  in  both  cases;  if  the  agitation 


/ 

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0MZ^Ex\xxxm20     ..AAX 
w^^Exxxxxx^.. 
7%6oO<^mM)<^^ 


JO     40      50     60     10      «0 
Percent  Saturated  0>ytcri 


20     JO     40     50     60     10 

Percent  Saturated  Glycerines 


FIG.  40w.— Runs  C  &  F.      FIG.  40^.— Runs  G  &  H.       FIG.  40/cfc .— Runs  I  &  J. 

is  really  better  at  this  speed  in  the  large  machine,  the  effect  of  the  increase 
in  size  on  the  path  of  hydrogenation  s  in  the  opposite  direction  to  the  effect  of 
increased  ag'tation. 

INFLUENCE  OF  MATERIAL  OF  CATALYZER 

When  some  other  catalyst  than  nickel  is  used  as  in  Experiment  K,  in  which 
1  per  cent  palladium  (in  PdCl2,  method  of  Paal  patent*)  acted  as  catalyzer, 
the  hydrogenation  curve  is  found  to  have  the  same  general  characte  i  tics  as 
those  described  before.  Bubbling  apparatus  was  used,  a  temperature  of  135°  C. 
and  atmospher  c  pressure.  No  experiment  using  nickel  catalyzer  is  available  to 
compare  directly  with  it. 

EXPERIMENT  WITH   PALLADIUM   AS   CATALYZER 


IODINE  NUMBER. 

PERCENTAGES  CALCULATED. 

Run  Sample. 

Fat. 

Liquid  Fatty 
Acid. 

Saturated 
Glycerides. 

Olein. 

Linolin. 

Ko 

108.4 

142.8 

20.6 

33.5 

45.9 

1 

89.1 

125.0 

25.5 

46.0 

28.5 

2 

76.6 

113.1 

29.2 

52.8 

18.0 

3 

64.5 

97.1 

30.6 

63.8 

5.6 

4 

53.0 

90.3 

38.6 

61.3 

0.1 

*Carl  Paal,  U.  S.  Patent  No.  1,023,753,  April  16,  1912.     An  equivalent  amount  of 
solid  Na2COs  is  used  as  a  neutralizing  agent. 


METHODS   OF   HYDROGEI^ATION'  Ml 


SUMMARY  OF  HYDROGENATION  CURVES 

To  summarize  the  conclusions  from  the  preceding  experiments,  it  appears 
that  the  chemical  character  of  a  partial  y  hydrogenated  oil  is  determined  by  the 
conditions  of  the  hydrogenation.  Thus  to  obtain  a  product  of  the  same  iodine 
number  as  another  but  relatively  higher  in  saturated  glycerides  and  linolin, 
the  operating  conditions  should  compare  as  follows  with  those  in  the  other  case: 
temperature  lower,  pressure  higher,  agitation  more  vio  ent  and  percentage  catalyzer 
greater.  It  is  interesting  to  note  that  it  s  possible  to  hydrogenate  the  linolin 
to  olein  with  only  the  slightest  increase  in  saturated  glycerides  by  operating  at  a 
high  temperature,  low  pressure  and  low  agitation,  and  using  only  a  small  amount 
of  catalyzer. 

II.  CHANGES  IN  CHEMICAL  CONSTANTS  OP  OIL  DURING  HYDROGENATION 

Of  all  the  "  chemical  constants  "  of  cottonseed  oil,  the  iodine  number  (with 
its  variations,  the  "  hydrogen  number,"  Maume"ne  number  and  heat  of  bromina- 
tion),  is  the  only  one  which  is  changed  markedly  by  hydrogenation.  Saponifica- 
tion  value,  acetyl  value,  Reichert-Meissl  number  and  percentage  of  free  fatty 
acids  change  either  not  at  all,  or  only  slightly. 

The  drop  in  iodine  number,  however,  is  one  of  the  most  striking  effects  of 
i.  ydrogenation,  and  it  has  been  commonly  used  in  the  past  to  indicate  the 
progress  of  the  reaction.*  Fokin  concludes,  from  a  study  of  the  hydrogen 
absorption,  that  "  the  reduction  procedure  is  included  in  the  category  of  mono- 
molecular  reactions,"  but  notices  that  the  curves  "  often  show  a  straightening 
out  toward  the  abscissa  axis."  He  comes  to  the  conclusion  that  the  conditions 
which  determine  the  shape  of  the  curve  are:  (a)  the  velocity  of  diffusion  of  the 
gas  (presumbly  through  the  oil);  (b)  the  condition  of  the  catalyzing  surface; 
and  (c)  the  presence  of  catalyzer  poisons.  Very  similar  conclusions  were  pub- 
lished recently  by  Boeseken,t  but  most  of  his  work  was  on  organic  compounds 
of  lower  molecular  weight  than  the  oils. 

Pressure.  Early  investigators  appreciated  the  fact  that  the  hydrogenation 
reaction  is  accelerated  by  pressure,  and  Moore,  Richter  and  Van  Arsdel  state 
that,  so  far  as  is  kno  ,vn,  all  of  the  commercial  oil-hardening  processes  are  carried 
out  at  gas  pressures  ranging  from  20  to  150  Ib.  or  even  higher.  Comparison  of 
the  two  curves  of  Fig.  40M  shows  that  the  time  required  to  reduce  the  iodine 
number  of  the  oil  to  any  specified  figure  is  roughly  cut  in  half  by  doubling  the 
pressure,  i.e.,  in  these  experiments  the  rate  of  hydrogenation  was  approximately 
proportional  to  the  hydrogen  pressure. 

Temperature.  It  is  likewise  well  known  that  the  hydrogenation  reactions  in 
oil  have  a  positive  temperature  coefficient,  i.e.,  the  rate  is  greater  the  higher 
the  temperature,  although  the  thermal  decomposition  of  the  oil  sets  an  upper  limit 
to  the  available  range  at  about  250°  C.  The  hydrogenation  reactions  in  oil  have 
a  positive  temperature  coefficient  in  the  range  between  35°  and  somewhat  above 

*Paal-Roth,  Ber.,  41,  2282-2291;  Fokin,  Z.  angew.  Chem.,  22,  1451-9,  1492-1502; 
Bomer,  Z.  Nahr.  Genussm.,  24,  104-113. 

Paal  and  his  co-workers,  and  Fokin  recorded  the  volume  of  hvdrogen  absorbed 
at  various  stages  of  the  process,  thereby  determining  directly  the  amount  of  satura- 
tion which  had  taken  place,  instead  of  indirectly  by  means  of  the  iodine  number. 

t  Rec.  trav.  chim.,  XXXV,  1916,  260-287. 


HYDROGENATION  OF  OILS 


200°  C. — possibly  up  to  240°  C.,  but  as  may  be  seen  from  a  study  of  the  curves 
of  Fig.  40mm,  this  coefficient  drops  consistently  as  the  temperature  rises.  Thus 
for  the  range  of  temperatures  35°  to  125°  the  time  required  to  reach  a  certain 
iodine  number  is  on  the  average  decreased  about  35  per  cent  for  each  10°  rise 
in  temperature,  while  for  the  range  160°  to  200°  this  coefficient  is  less  than  20 
per  cent.  Since  the  commercial  processes  nearly  all  operate  at  temperatures  of 
160°  to  180°,  it  is  evident  that  no  material  gain  in  time  could  be  made  by  the 
use  of  higher  temperatures,  and  the  point  of  maximum  economy  is  probably 
being  realized. 


JJ 


Tim*  ,  Minutes 


FIG.  mi. 


% 


FIG.  40mm. 


Time,  Houra 

FIG.  4Qnn. 


Agitation.  The  increase  in  velocity  of  reaction  due  to  increased  agitation  of 
oil  and  catalyzer  with  hydrogen  is  shown  in  Fig.  40nn.  In  this  case  an  increase  of 
about  100  per  cent  in  the  volume  of  hydrogen  supplied  increased  the  velocity 
of  the  reaction  800  to  1000  per  cent.  In  apparatus  of  this  type  handling 
charges  of  commercial  size  it  is  not  usual  to  cause  such  violent  agitation  as  is 
easily  brought  about  in  a  2-litre  flask,  and  it  is  doubtful  whether  doubling  the 
hydrogen  supply  would,  on  a  large-scale,  more  than  double  the  reaction-rate.  The 
importance  of  efficient  agitation,  or  of  intimate  commixture  of  the  oil,  catalyzer 
and  hydrogen,  has  apparently  been  realized  by  nearly 
all  of  the  workers  in  this  field,  as  witness  the  patent 
files,  but  there  is  no  observation  recording  such  a 
great  increase  in  agitation  as  the  above,  brought  about 
by  such  simple  means. 

Catalyzer.  As  in  practically  all  catalytic  reactions, 
the  speed  of  hydrogenation  is  increased  as  the  percent- 
age of  catalyzer  is  raised. 

The  time  required  to  reach  a  given  iodine  number 
is  roughly  proportional  to  he  percentage  of  catalyzer 
(Fig.  40oo).  Considerations  of  outlay  required  for 
catalyzer  preparation  and  recovery  limit  the  amount 
used  in  commercial  batch  processes,  however,  to  1,  or 
at  most,  2  per  cent.  When  a  very  good  grade  of 

refined  oil  is  used,  as  little  as  0.1  per  cent  nickel  is  common  practice,  high  pres- 
sure and  agitation  being  relied  upon  to  reduce  the  time  consumed. 

SUMMARY  OF  IODINE  NUMBER-TIME  CURVES 

To  summarize,  increasing  the  pressure,  temperature,  agitation  or  amount  of 
catalyzer  will  increase  the  rate  at  which  cottonseed  oil  is  hydrogenated.     This 


3o 

Time,  MinuTes 

FIG.  40oo. 


METHODS   OF   HYDROGENATION 


103 


increase  in  rate  is  roughly  proportional  to  the  increase  in  pressure  or  amount  of 
catalyzer,  while  raising  the  temperature  10°  in  the  region  of  common  practice, 
160°  to  180°,  increases  the  rate  only  about  20  per  cent.  Increase  in  agitation 
(difficult  to  measure  quantitatively)  produces  a  marked  increase  in  the  reaction- 
rate. 

III.  CHANGES  IN  PHYSICAL  CONSTANTS  OF  OIL  DURING  HYDROGENATION 

The  most  striking  effect  of  the  hydrogenation  of  an  oil  is,  of  course,  the 
gradual  increase  in  solidity,  with  the  accompanying  change  in  such  physical 
constants  as  melting-point  and  titer. 

Melting-point.  Oil  was  hydrogenated  with  mechanical  agitation  of  108 
r.p.m.,  temperature  160°  C.,  pressure  20  lb.,  catalyzer  5  per  cent,  nickel  on  a 
carrier.  The  melting-point  and  iodine  number  were  among  the  constants  deter- 
mined on  each  sample,  and  these  constants  compared  as  follows : 

Mo  Mt  M2  Ms  M4  Ms  Me 

Melting-point,    °C 9.0      39.4      40.8      45.8      48.0      48.9      60.5 

Iodine  number 107      74.3      66.7      61.0      54.5      48.5        0.4 

There  can  be  no  doubt  that  while  the  two  ends  of  this  curve  remain  fixed, 
the  intermediate  points  are  capable  of  considerable  variation  from  the  curve, 
depending  on  the  conditions  of  hydrogenation.  We  have,  for  instance,  the  points 
A  and  B  on  Fig.  40pp.  Sample  A  was  made  by  one  of  the  "  cont  nuous  "  processes 
from  the  same  kind  of  cotton-oil,  while  Sample  B  was  made  at  a  very  high  tem- 
perature. 

Titer.  The  titer  of  an  oil  or  fat,  being  the  solidification-point  of  its  fatty 
acids,  might  be  expected  to  share  the  characteristic  of  the  melting-point  of  the 


C,/ 


lod. 


FIG.  40pp. 


"Time  ,  Houra 

FIG.  4Qqq. 


HO        80        TO        bo       SO       40       3« 

lod,r>o  Number 


FIG.  40rr. 


fat,  namely,  a  gradual  increase  of  hydrogenation.  It  is  found,  however,  to  show 
the  peculiarity  of  first  decreasing,  passing  through  a  minimum,  and  then  increas- 
ing steadily.  Cotton-oil  was  hydrogenated  with  5  per  cent  of  nickel,  on  a  car- 
rier, in  one  case  at  125°  C.,  and  in  the  other  at  200°  C.  Titer  and  iodine 
number  were  among  the  determinations  made  on  each  sample.  In  Fig.  40<?</  titer 
is  plotted  against  time  and  in  Fig.  40rr  against  iodine  number. 

The  apparently  anomalous  fact  that  the  addition  of  more  saturated,  higher 
melting  acids  at  first  lowers,  instead  of  raising  the  solidification  point  is  evidently 
due  to  the  existence  of  a  eutectic,  or  low  melting  mixture  of  the  components. 
According  as  the  path  hydrogenation  carries  the  composition  close  to  or  far 
from  this  point  the  minimum  attained  will  be  lower  or  higher.  From  Fig.  40rr 


104  THE  HYDROGENATION  OF  OILS 

it  is  evident  that  the  low-temperature  run  passed  closer  to  the  eutectic  point 
than  did  the  high-temperature  run.  Below  iodine  number  50  the  two  runs  were 
practically  identical,  as  would  be  expected  from  the  fact  that  since  linolin  has 
largely  disappeared  the  two  hydrogenation  curves  of  component  glycerides  cannot 
differ  very  greatly. 

IV.  RESPONSE  TO  HALPHEN  TEST 

Hydrogenated  cottonseed  oil  was  first  stated  by  Paal  and  Roth  *  to  give 
no  coloration  when  subjected  to  the  characteristic  Halphen  test  f  and  the  same 
statement  has  been  made  by  later  investigators.  The  amount  of  hydrogenation 
which  is  required  to  render  the  oil  just  incapable  of  responding  to  the  test  was 
investigated  by  Moore,  Richter  and  Van  Arsdel.  To  determine  that  point  a 
quantity  of  oil  was  hydrogenated  at  a  temperature  of  150°  to  160°  C.,  2  per 
cent  nickel  on  a  carrier  acting  as  catalyzer.  Samples  were  taken  (a)  of  the' 
original  oil,  (6)  of  the  mixed  oil  and  catalyzer  before  heating,  (c)  of  the  mixed 
oil  and  catalyzer  when  heated  to  150°  C.,  five  minutes  being  required  to  reach 
this  temperature,  (d)  after  three-minute  hydrogenation,  (e)  after  nine-minute 
hydrogenation,  and  (/)  after  fifteen-minute  hydrogenation.  A  similar  sample  of 
oil  was  heated  to  150°  to  160°  for  twenty  minutes  in  the  absence  of  any  hydro- 
gen or  catalyzer,  and  was  then  found  to  give  the  same  intensity  of  Halphen  test 
as  Sample  a.  The  other  samples  gave  tests  as  follows: 

Iodine 
Sample.  Number.  Result. 

6 104 . 9  Not  noticeably  diminished 

c 103 . 7  Distinctly  weaker  test 

d 102 . 7  Faint  test  in  3  minutes 

e 101 . 3  Faint  test  after  heating  1  £  hours 

/ 97 . 6  Negative  even  after  heating  If  hours 

A  drop  of  four  units  in  iodine  number  may  be  said  to  have  destroyed  the 
chromogenetic  substance. 

MISCELLANEOUS  PUBLICATIONS  ON  HYDROGENATION 

A  paper  by  Lessing  on  Catalysis  in  the  gas  industry  appears  in 
J.  Gas  Lighting,  1914,  127,  570-573;  see  also  J.  S.  C.  I.,  1914,  1193. 
Rivals  |  discusses  the  subject  of  oil  hydrogenation  quite  fully.  The 
hydrogenation  of  oils  and  fatty  compounds  is  described  by  Jaubert  § 
who  gives  an  outline  of  the  whole  industry,  including  a  discussion 
of  catalysis,  the  production  of  hydrogen  and  the  hydrogenation  of 
fats,  with  a  detailed  description  and  drawings  of  processes  used  by 
a  number  of  the  largest  concerns  in  the  world.  The  same  subject  is 
d'scussed  by  Ueno  who  refers  to  the  following  subjects:  hydrogena- 

*Paal  and  Roth,  Ber.,  42,   1909,   1541-1553. 

fJ.  A.  O.  A.  C.,  No.  3,  II,  1916,  313. 

JRev.  gen.  chem.,  18,  9-26,   1915 

§Rev.  gen.  chem.,  18,  117-33,  144-60,  1915. 

II  J.  Chem.  Ind.  Japan,  8,  545-65,  1915;    Chem.  Abs.,  1916,  535. 


METHODS   OF  HYDROGENATION  105 

tion  of  sardine  oil  on  a  semi-commercial  scale;  examination  of  the 
intermediate  products  of  hydrogenation ;  durability  of  the  activity 
of  nickel  and  revivification  of  spent  catalyzer;  hydrogenation  at 
low  temperatures;  and  the  relation  of  the  catalytic  activity  of  nickel- 
kieselguhr  catalyzer  to  the  proportions  of  the  nickel  and  its  carrier. 
A  description  of  the  Wilbuschewitsch  apparatus  and  its  manipula- 
tion for  the  manufacture  of  hardened  oils  and  of  catalyzers  is  given 
by  Schicht*  Sjoquist,f  describes  the  Wilbuschewitsch  process  and 
some  experiments  made  in  the  laboratory  on  the  hardening  of  fats. 
The  catalytic  hardening  of  fats  is  discussed  by  Siegmund.  t  An 
address  given  by  Hertzog  on  the  subject  of  fat  hardening  appears  in 
the  Seifensieder  Zeitung,  43,  589.  §  A  comprehensive  account  of  the 
history  of  the  hardening  process,  properties  of  hardened  fats  and 
their  utilization  for  various  technical  purposes  and  for  food  is  fur- 
nished by  Fahrion.||  The  hydrogenation  of  fats  is  reviewed  by  Red- 
grove,^  and  the  review  includes  a  discussion  of  the  following  topics: 
historical  catalysts,  apparatus,  and  uses.  No  new  material  is  intro- 
duced, but  the  patent  literature  is  largely  drawn  on.  Klimont  **  has 
published  a  paper  on  technical  oil  hardening  apparatus.  An  interesting 
and  useful  summary  of  some  of  the  more  recent  applications  of  catalysis, 
especially  in  inorganic  chemistry,  is  published  by  Jobling  in  a  book 
entitled  "  Catalysis  and  Its  Industrial  Applications,"  Blakiston's  Son 
&  Company,  1916.  The  book  contains  a  brief  chapter  on  hydro- 
genation and  catalytic  material  used  in  carrying  out  hydrogenation 
processes.  According  to  the  Journal  of  Industrial  and  Engineering 
Chemistry,  1918,  p.  158,  the  Tariff  Commission  of  the  United  States, 
in  making  an  inquiry  in  regard  to  chemical  industries,  proposes  to 
study,  as  one  subject,  the  development  or  invention  in  the  United 
States  or  abroad  of  new  or  improved  processes  which  are  likely  to 
influence  the  conditions  of  international  competition;  for  example, 
the  hydrogenation  of  fatty  oils. 

In  a  German  patent  application  filed  June  14,  1913,  by  the  Bremen 
Besigheimer  Oelfabriken,  the  claim  is  made  for  the  transformation 
of  drying  oils  such  as  soya  bean  oil,  sunflower  oil  and  linseed  oil  to 

*Seifen.  Ztg.,  1914,  1189. 

t  Deut.  Parfum.  Ztg.,  1916,  7;  Seifen.  Ztg.,  1916,  234  and  257;  Chem.  Zentr.,  1916, 
I,  1206. 

JOesterr.  Chem.  Ztg.,  1916,   19,  88. 

§See  also  pharm.  Post.  49,  309;    Chem.  Zentr.,  1916,  I,  1282,  II,  776. 

||  Naturwschn.  4,  283-7;  Chem.  Zentr.,  1916,  II,  285;  Chem.  Abs.,  1917,  2157; 
Chem.  Umschau,  1916,  23,  155. 

f  Chem.  Trade  J.,  60,  273. 

**Chem.  Apparatur,  1916,  3,  Nos.  3  and  4;    Seifon.  Ztg.,  1916,  168. 


106  THE  HYDROGENATION  OF  OILS 

non-drying  oils  by  partial  hydrogenation.*  Hydrogen  is  added  until 
a  sample  tested  with  the  refractometer  shows  that  the  oil  has  lost 
its  drying  properties.  A  careful  review  on  the  hydrogenation  art 
is  presented  by  Bergius  together  with  certain  figures  as  to  cost  of 
hydrogen  and  catalyzer,  which  are  of  interest.!  Ellis  has  reviewed 
the  progress  of  the  industry  in  Oil,  Paint  &  Drug  Reporter,  Oct.  26, 
1914,  p.  18.  A  paper  by  Jaubert  on  the  hydrogenation  of  oils  and 
fats  appears  in  Memoires  de  la  societe  des  ingenieurs  civils  de  France, 
Vol.  67  (1915),  No.  7-12,  305-353.  In  a  review  by  Fabris  of  the 
fatty  oil  industry  J  the  subject  of  hardened  or  hydrogenated  oils  is 
discussed.  L'Industrie  Chimique,  Apr.,  1916,  furnishes  data  on 
various  oil  hardening  plants.  Laboratory  experiments  on  oleic  acid 
vapor  in  a  stream  of  hydrogen  under  reduced  pressure,  on  liquid  oleic 
acid  and  hydrogen  under  various  pressures,  and  on  the  reduction  of 
cottonseed  oil  by  hydrogen  under  high  pressures  are  reported  by 
Shaw§  (see  p.  26).  To  effect  reaction  between  gases  and  liquids 
Andersen  proposes  the  use  of  what  he  terms  "  porous  metals  "  and 
their  alloys  as  catalysts,  such  as  iron,  uranium,  tungsten,  etc.  The 
walls  of  the  vessel  in  which  the  reaction  takes  place  may  be  coated 
with  the  porous  material. ||  Robson  If  reports  that  oils  obtained  from 
the  waste  lyes  produced  in  the  manufacture  of  sulphate  pulp  for  paper- 
making  are  sent  to  England  to  be  hydrogenated.  Robson  comments  on 
the  early  history  of  hydrogenation  of  fatty  oils,  especially  the  Nor- 
mann  patent.  The  treatment  of  wool  grease  with  hydrogen  to  im- 
prove its  quality  is  proposed  by  Ellis.**  A  method  of  adding  the 
elements  of  water  to  unsaturated  organic  acids  is  advanced  by  Schicht 
A.  G.,and  Grim  ft  which  consists  in  heating  a  salt  of  the  acid,  e.g., 
linolic  acid  under  pressure,  with  water,  in  presence  of  a  small  quan- 
tity of  an  alkaline  substance.  In  lieu  of  free  hydrogen  a  body  capable 
of  liberating  hydrogen  on  contact  with  a  catalyzer  is  proposed  by 
Kayser  Jt  for  hydrogenating  fatty  oils.  Borneol  is  recommended  for 
this  purpose.  Boehringer  and  Soehne  §§  hydrogenate  unsaturated 

*Seifen.  Zeitung,  1915,  No.  3,  51. 

fZeit.  f.  angew.  Chem.,  1914,  525. 

jchem.  Abs.,  1915,  2602;    Ann.  chim.  applicata,  1915,  349. 

§J.  S.  C.  I.,  1914,  771. 

||  J.  S.  C.  I.,  1913,  999,  French  Patent  No.  457,569,  May  7,  1913,  English  Patent 
No.  7,839,  April  3,   1913,  Seifen.  Ztg.,  1914,   1174. 

f  Drugs,  Oils  and  Paints,  1914,  211. 
**  U.  S.  Patent  No.  1,086,357,  February  10,  1914. 
ft  German  Patent  No.  287,660,  July  16,  1914;    J.  S.  C.  I.,  1916,  186. 
UJ.  S.  C.  I.,  1915,  560;    U.  S.  Patent  No.  1,134,746,  April  6,  1915. 
§§Chem.  Abs.,   1916,    1080,    1780;    British  Patent  No.  21,883,   November  2,    1914; 
Swiss  Patent  No.  71,689,  February  1,  1916. 


METHODS   OF  HYDROGENATION  107 

substances  in  solution  or  suspension  in  water  or  alcohol,  using  a  cata- 
lyzer of  the  nickel  group.  In  a  Japanese  patent  issued  to  the  Hydroil 
Co.,  Ltd.,*  unsaturated  fatty  acids,  their  glycerides,  and  other  esters, 
are  treated  with  hydrogen  or  hydrogen-containing  gases  in  the  pres- 
ence of  heated  powdered  metallic  oxides,  by  means  of  which  their 
saturated  compounds  are  obtained.  Schmidt  and  Blankenhorn  f 
propose  to  carry  out  catalytic  hydrogenation  by  employing  as  the  re- 
ducing gas,  carbon  monoxide  admixed  with  water  vapor.  The  process 
is  recommended  in  connection  with  the  reduction  of  nitrobenzene  to 
aniline.  Barnitzf  observes  that  the  consumption  of  hydrogen  by  fatty 
oils  varies  usually  between  2870  and  4300  cu.ft.  per  ton.  It  has  been 
stated  §  that  1  ton  of  oleic  acid  requires  2800  cu.ft.  of  hydrogen,  while 
a  like  amount  of  triolein  calls  for  2680  cu.ft.  of  the  gas.  A  process  for 
solidifying  fats,  fatty  oils,  mineral  waxes,  or  mineral  oils  and  converting 
them  into  dry  pulverulent  products  by  means  of  malt  extract  or  malto- 
dextrin  is  described  by  Hamburg.  ||  An  apparatus  for  hardening  oil 
is  described  by  Uchida^f  and  comprises  the  following  elements:  a  con- 
tainer for  the  fats  and  oils,  a  supply  pipe  for  hydrogen,  a  device  for 
breaking  up  the  current  of  hydrogen  into  bubbles,  and  discharge  pipes 
for  the  waste  gases.**  A  pamphlet  giving  a  brief  survey  of  oil  hardening 
has  been  published  by  Fahrion,ft  L'Industrie  Chimique  (April,  1916) 
reviews  the  subject  of  oil  hardening. 

A  process  of  hydrogenating  oils  which  has  been  devised  by  Walker  Jt  involves 
the  use  of  a  closed  receptacle  in  which  a  body  of  oil  to  be  hardened  ic  placed.  This 
oil  contains  finely-divided  catalyzer.  The  receptacle  contains  a  shelf  supporting 
a  bed  of  catalyzer  which  is  placed  above  the  body  of  the  oil.  The  mixture  of  oil 
and  finely-divided  catalyzer  is  pumped  from  the  bottom  of  the  receptacle  to  the 
top  where  it  is  sprayed  upon  the  bed  of  the  catalyzer  and  passing  there  through 
collects  in  the  body  of  oil  beneath.  The  latter  is  stirred  by  an  agitator  while  hydrogen 
is  blown  through  the  oil.  The  unabsorbed  gas  is  withdrawn  from  the  top  of  the  recep- 
tacle and  is  passed  through  a  condenser  to  remove  moisture.  It  is  then  returned 
to  the  bottom  of  the  receptacle.  Thus  both  the  oil  and  the  gas  are  constantly 
circulated  through  the  oil  container.  A  compilation  of  patents  of  the  United  States, 
Great  Britain  and  Germany,  relating  to  the  manufacture  of  butter  substitutes, 
hydrogenated  oils  and  milk  products  having  substituted  fats,  has  been  prepared 
by  Mock  &  Blum,  patent  lawyers,  220  Broadway,  New  York  City, 

*  No.  30,057,  September  19,  1916. 

t  U.  S.  Patent  No.  1,237,828;    August  21,  1917. 

J  Met.  Chem.  Eng.,  April  1,  1916. 

§  J.  S.  C.  I.,  1914,  1140. 

||  French  Patent  No.  466,419,  December  20,  1913;    J.  S.  C.  I.,  1914,  603.     See  also 
British  Patent  No.  29,481,   1912;    J.  S.  C.  I.,   1913,  672. 

1  Japanese  Patent  No.  31,304,  July  12,  1917;    Chem.  Abs.,  1918,  234. 
**  See  also  Asahi  Electrochemical  Co.,  Japanese  Patent  No.  31,393,  August  7,  1917; 
Chem.  Abs.,  1918,  234. 

ft  Die  Hartung  der  Fette,  Braunschweig,  1915. 
S.  Patent  1,276,290,  August  20,  1918. 


CHAPTER  IV 

CATALYZERS  AND  THEIR  ROLE  IN  HYDROGENATION 

PROCESSES 

.  THE  BASE  METALS  AS  CATALYZERS 

Catalyzers,  those  bodies  which  modify  reaction  velocity  without 
stoichiometrical  participation  in  the  reaction,  are  destined  to  find 
another  important  industrial  application  in  the  hardening  of  oils.* 

For  present  purposes  a  catalyzer  may  be  simply,  though  less  ac- 
curately, defined  as  a  material  or  "  exciter  "  which  brings  about  a 
reaction  between  substances  otherwise  incapable  of  reacting,  the  cata- 
lyzer itself  at  the  end  of  the  reaction  being  unchanged.  Thus  fatty 
oil  and  hydrogen  do  not  unite  readily  unless  nickel  or  some  other 
catalytic  body  is  present  to  serve  as  a  carrier  or  go-between  to  bring 
about  the  reaction. 

The  previous  illustrations  show  the  variety  of  methods  proposed 
for  mingling  oil,  hydrogen  and  catalyzer.  Among  these  are  several 
of  excellent  efficiency.  But,  after  all,  the  virility,  so  to  speak,  of  the 
process,  depends  on  the  catalyzer.  With  a  powerful  catalyzer  the 
hydrogenation  of  oils  becomes  a  rapid,  simple  procedure;  almost,  it 
sometimes  seems,  independent  of  the  nature  of  the  hydrogenating 
apparatus. 

Catalyzers  recognized  as  useful  for  the  purpose  are  nickel  and  palla- 
dium, although  platinum,  copper,  iron  and  other  metals  have  been 
used  to  some  extent.  Nickel  oxide,  as  stated,  has  been  employed  by 
Bedford  and  Ipatiew.  Wimmer  recommends  organic  salts  of  nickel, 
such  as  the  formate,  acetate  or  lactate. 

As  nickel  is  probably  the  most  important  of  these  catalyzers,  in 
view  of  its  efficiency  and  relatively  low  cost,  it  will  be  first  considered.! 

*  Abel.  Zeitsch.  f.  Elektrochem.  (1913),  933-951,  gives  a  bibliography  on  catal- 
ysis. Conroy,  J.  S.  C.  I.,  1902,  302,  discusses  the  industrial  side  of  catalysis.  See 
also  Jobling,  Chem.  World  (1914),  17;  Agulhon,  J.  Agr.  tropicale  (1913),  375;  Stem 
on  Catalysis,  Fortschritte  d.  Chem.  Phys.  u.  Phys.  Chem.  (1913),  249.  A  very  good 
review  of  the  subject  of  oil  hardening  and  the  catalyzers  employed  for  the  purpose 
is  contributed  by  Meyerheim,  Fortschritte  d.  Chem.  Phys.  u.  Phys.  Chem.  (1913), 
293.  Another  review  appears  in  the  Bulletin  of  the  Imperial  Institute  (1913),  660. 

f  Nickel  is  recommended  as  the  best  catalyzer  for  hardening  whale  oil,  Seifen. 
Ztg.  (1913),  1412. 

108 


CATALYZERS  109 

The  preparation  of  an  effective  nickel  catalyzer  requires  considerable 
care.  The  oxide  or  hydrate  of  nickel  is  first  obtained  by  ignition  of 
nickel  nitrate,  or  precipitation  of  nickel  hydrate  from,  say,  a  nickel 
sulfate  solution  by  the  addition  of  an  alkali.  Obtained  in  this  or  in 
any  other  suitable  manner,  the  next  step  is  the  reduction  to  metallic 
nickel.  For  this  purpose  the  nickel  is  placed  in  a  receptacle  which 
may  be  heated  controllably,  and  hydrogen  gas  is  passed  over  the  mass 
at  a  temperature  ranging  from  250°  to  500°  C.  or  so,  until  water  is  no 
longer  evolved. 

The  most  sensitive  catalyzers  are  obtained  by  reduction  at  the 
lowest  possible  temperatures.  Nickel  begins  to  reduce  below  220°  C., 
but  at  270°  C.  the  reduction  is  not  complete  even  after  long  duration 
of  exposure  to  hydrogen.  A  temperature  of  300°  to  350°  C.  gives 
fairly  complete  reduction  and  is  a  satisfactory  working  range.  The 
lower  the  temperature  at  which  the  nickel  is  reduced,  the  more  sen- 
sitive it  is  to  various  external  influences,  hence  the  preparation  of 
this  catalyzer  should  be  conducted  not  only  with  respect  to  degree  of 
activity,  but  also  with  respect  to  longevity. 

Nickel  is  easily  poisoned  by  chlorine  and  by  sulfur  in  the  sulfide 
form.*  The  author  has  not  experienced  unfavorable  results  from  the 
use  of  hydrogen  gas  passed  through  a  wash  bottle  containing  concen- 
trated sulfuric  acid  and  then  conveyed  directly  to  the  catalyzer  and 
oil.  Traces  of  the  acid  were  entrained  by  the  gas,  but  the  catalyzer 
remained  in  active  condition  during  about  two  weeks  usage  under 
these  conditions. 

Copper  is  much  less  sensitive  to  poisons  than  nickel,  but  on  the 
other  hand  it  is  much  less  active. f 

Catalyzer  made  from  the  heavier  forms  of  the  oxide  without  sup- 
porting material,  weight  for  weight,  is  hardly  as  efficient  as  when  the 
active  surface  is  increased  by  the  use  of  a  carrier.  Hence  we  find 
many  proposals  for  the  production  of  catalyzers  with  a  great  diversity 
of  carriers  and  extenders,  ranging  from  pumice  stone  and  kieselguhr 
to  charcoal  and  sawdust. 

*  The  albumin  contained  in  animal  and  vegetable  fats  and  oils  is  a  source  of 
sulfur-containing  gases  (Bedford  and  Erdmann,  Jour.  f.  prakt.  Chem.,  1913,  426). 

t  Mailhe  (Rev.  gen.  sci.,  24,  650)  describes 'the  scientific  and  technical  uses  of 
active  nickel  as  catalyst  in  the  reduction  of  organic  compounds  and  in  the  hydro- 
genation  of  oils.  He  also  discusses  the  catalytic  properties  of  finely-divided  copper 
and  the  commercial  possibilities  of  metallic  oxides  (especially  ThO2)  as  catalytic 
agents  in  processes  requiring  elimination  of  water  (or  water  and  hydrogen,  depending 
on  temperature)  from  organic  compounds.  Drawings  are  given,  showing  forms  of 
apparatus.  Much  stress  is  laid  on  the  maintenance  of  proper  temperatures  and  on 
the  use  of  pure  hydrogen. 


110  THE  HYDROGENATION  OF  OILS 

After  reduction  of  nickel,  as  above,  it  should  be  kept  out  of  contact 
with  air  as  it  is  usually  extremely  pyrophoric  and  quickly  loses  much 
of  its  efficiency  on  exposure  to  the  air.*  Consequently  when  treating 
oil  with  such  a  catalyzer,  it  is  advisable  to  free  the  treating  apparatus 
from  air  by  flushing  with  hydrogen;  also  it  is  sometimes  beneficial  to 
heat  the  oil  and  bubble  hydrogen  through  it  for  a  short  time  prior  to 
the  introduction  of  the  catalyzer. 

The  use  of  nickel  as  a  contact  body  by  Mond,f  in  1888,  is  of  historical 
interest  in  view  of  present  developments.  Mond  found  that  if  car- 
bonic oxide  or  gaseous  hydrocarbons  be  brought  into  contact  with 
metallic  nickj^'at  a  temperature  of  350°  to  400°  C.,  or  with  metallic 
cobalt  at  4$T  to  450°  C.,  decomposition  takes  place  into  carbon  and 
carbonic  acid  or  hydrogen,  the  carbon  combining  with  the  metal.  If 
now  steam,  at  a  moderate  temperature,  be  introduced,  this  carbon 
combines  with  oxygen  to  produce  carbonic  acid,  with  simultaneous 
formation  of  free  hydrogen.  These  various  reactions  take  place 
simultaneously  when  the  steam  is  passed  through  the  apparatus  along 
with  the  carbonic  oxide  or  hydrocarbon,  the  ultimate  products  being 
carbonic  acid  and  hydrogen.  The  former  can  be  eliminated  by  any 
suitable  means,  such  as  by  washing  with  milk  of  lime.  The  cobalt 
or  nickel  surfaces  may  be  obtained  by  impregnating  pumice  stone  with 
a  solution  of  the  metal,  and  reducing. | 

The  Mond  and  Langer  British  Patent  12,608,  of  1888,  is  entitled  Improvements  in 
Obtaining  Hydrogen.  From  the  specification  the  following  is  quoted: 

"By  the  distillation  or  incomplete  combustion  in  the  presence  or  in  the  absence 
of  steam,  oil,  lignite,  wood,  coke,  animal  carbon  or  organic  substances  in  general, 
gases  are  obtained  which  consist  chiefly  of  hydrogen,  carburets  of  hydrogen,  mon- 
oxide and  dioxide  of  carbon  and  a  greater  or  less  quantity  of  nitrogen.  The  object 
of  our  invention  is  to  eliminate  from  these  gases  the  monoxide  of  carbon  and  the 
carburets  of  hydrogen,  and  at  the  same  time  to  increase  the  amount  of  hydrogen 
contained. 

"  If  a  mixture  of  monoxide  of  carbon  or  carburet  of  hydrogen  and  steam  be  heated 
to  white  heat  in  the  presence  of  firebricks  or  of  oxide  of  iron,  the  latter  is  decomposed 
and  the  carbon  of  the  gases  is  oxidized  to  carbon  dioxide  and  the  hydrogen  set  at 
liberty.  The  high  temperature  required  for  this  reaction  renders  it  of  little  profit 
and  it  is  difficult  to  produce  it  on  an  industrial  scale.  We  have  found  that  if  mon- 
oxide of  carbon  and  hydrocarburets  be  placed  in  contact  with  metallic  nickel  or 

*  Wimmer  and  Higgins  (Seifen.  Ztg.  (1913),  556)  prepare  catalyzer  by  reducing 
the  active  material  while  it  is  enveloped  in  a  protecting  material,  oil  being  recom- 
mended for  this  purpose. 

t  British  Patent  12,608,  Sept.  1,  1888. 

J  The  use  of  nickel  in  the  catalytic  reduction  of  carbon  monoxide  to  methane  is 
set  forth  in  U.  S.  Patents  to  Elworthy  738,303,  Sept.  8,  1903;  777,848,  Dec.  20, 
1904;  and  943,627,  Dec.  14,  1909. 


CATALYZERS  111 

cobalt  at  a  temperature  not  exceeding  a  red  heat,  these  gases  are  decomposed  into 
carbon  and  dioxide  of  carbon  on  the  one  hand  and  hydrogen  on  the  other;  the  free 
carbon  so  formed  placed  in  contact  with  steam  at  a  moderate  temperature  decom- 
poses the  latter  and  forms  dioxide  of  carbon  and  hydrogen. 

"  If  the  steam  and  the  gases  are  mixed  from  the  commencement,  the  two  reactions 
take  place  simultaneously  and  the  result  is  a  gas  practically  free  from  monoxide  of 
carbon  and  hydrocarburets.  It  is  quite  possible  to  attain  our  object  by  carrying 
out  consecutively  the  two  above-mentioned  reactions  and  by  repeating  them  con- 
tinually with  the  same  quantity  of  nickel  and  cobalt  which  will  always  be  regen- 
erated. We  prefer,  however,  to  carry  out  these  two  reactions  simultaneously, 
at  the  same  time  employing  the  least  possible  amount  of  nickel  and  cobalt;  with 
this  object  we  spread  the  aforesaid  metals  on  an  indifferent  refractory  and  porous 
material.  For  example,  we  saturate  pieces  of  pumice  stone  with  a  solution  of  chloride 
of  nickel  or  cobalt,  dry  and  reduce  at  a  higher  temperature  with  hydrogen. 

"In  carrying  out  our  invention  industrially  we  lead  the  gases  with  an  excess  of 
steam  into  retorts  or  cylinders  fixed  in  a  suitable  furnace  and  containing  pieces  of 
pumice  stone  impregnated  with  nickel  or  cobalt  as  above  mentioned.  When  nickel 
is  used,  the  reaction  takes  place  at  a  temperature  of  350°  to  400°  C.  If  cobalt  be 
used,  at  a  temperature  of  400°  to  450°  C.  The  reactions  which  take  place  between 
the  gas  and  the  steam  produce  heat  so  that  the  given  temperature  once  reached  the 
reaction  goes  on  of  itself  without  need  of  external  heating. 

"It  may,  however,  be  advantageous  to  use  gases  or  steam  or  both,  heated  to  a 
suitable  temperature  before  they  are  placed  in  the  retorts.  The  gases  so  treated 
contain  little  or  no  monoxide  of  carbon.  The  carbonic  acid  can  be  separated  in  any 
known  manner,  such  as  by  passing  the  gases  through  lime  or  caustic  alkali. 

"  The  foregoing  process  differs  entirely  from  the  plan  of  using  an  easily  reduced 
oxide  and  oxidizing  the  carbonic  oxide  or  hydrocarbons  by  means  of  that  oxide  at 
a  bright  red  heat,  as  in  our  case  no  oxide  is  used,  but  a  metal  having  but  little  affin- 
ity for  oxygen,  but  a  considerable  affinity  for  carbon.  The  metal  deprives  the 
carbonic  oxide  of  a  part  of  its  carbon  and  gives  the  latter  up  to  the  oxygen  of  the 
steam.  This  is  done  at  a  heat  much  below  that  at  which  oxide  of  iron  or  other  like 
oxide  would  give  up  its  oxygen." 

Mond  and  Langer  lay  claim  to  the  process  of  obtaining  hydrogen  by  means  of 
gases  containing  carbon  monoxide  with  or  without  hydrocarbons  which  consists  in 
treating  such  gases  with  metallic  nickel  or  cobalt  and  with  steam  and  separating 
from  the  hydrogen  the  carbonic  acid  resulting  from  such  a  treatment. 

They  also  claim  the  use  of  pumice  stone  or  other  similar  porous  substance  impreg- 
nated with  one  or  more  salts  of  cobalt  or  nickel  so  as  to  provide,  when  reduced,  an 
extended  metallic  surface  with  only  a  small  amount  of  actual  metal. 

These  extracts  are  given  because  of  the  use  by  Mond  and  Langer,  in  1888,  of 
reduced  nickel  or  cobalt  on  porous  refractory  material  for  catalytic  purposes,  although, 
to  be  sure,  the  object  of  the  process  was  to  produce  hydrogen  rather  than  to  cause 
its  combination  with  unsaturated  bodies. 

Carbon  and  hydrogen  combine  with  difficulty,  especially  to  form  methane.  At 
the  ordinary  pressure  in  the  presence  of  nickel  oxide,  reduced  nickel  or  a  mixture 
of  nickel  and  alumina,  and  up  to  625°  C.,  there  is  no  formation  of  methane.  Under 
great  pressures  its  synthesis  only  occurs  above  500°  C.  in  the  presence  of  the  above 
substances  or  mixtures,  and  so  much  the  better  as  the  temperature  becomes  greater. 
In  the  presence  of  water  and  nickel,  methane  is  decomposed  at  500°  C.  into  hydrogen 
and  carbonic  acid.  The  inverse  reaction,  i.e.,  reduction  of  carbonic  acid  to  methane 


112  THE  HYDROGENATION  OF  OILS 

in  the  presence  of  nickel  and  an  excess  of  hydrogen  at  ordinary  pressure,  occurs  at 
450°  C.  Results  are  the  same  with  nickel  oxide.  (Chem.  Trade  Jour.,  Oct.  25,  1913, 
414.) 

At  ordinary  pressure  no  methane  is  formed  by  combination  of  its  elements  in 
the  presence  of  catalyzers  such  as  nickel  or  nickel  oxide,  but  under  high  pressures 
and  at  a  temperature  of  510°  to  520°  C.,  methane  is  formed.  (Ipatiew  Chem.  Ztg. 
Rep.  (1914),  15.) 

Acetylene  is  converted  into  ethylene  by  treatment  with  hydrogen  under  pres- 
sure in  the  presence  of  catalyzers.  The  Elektro  Chemische  Werke  G.  m.  b.  H. 
(Zeitsch.  f.  angew.  Chem.  (1913),  ref.  644)  find  that  the  production  of  ethylene  from 
acetylene  and  hydrogen  on  a  commercial  scale  is  difficult,  due  to  the  gradual  loss 
in  the  efficiency  of  the  catalyzer.  Even  though  the  usual  precautions  are  taken  to 
remove  the  recognized  poisons,  such  as  hydrogen  sulfide,  sulfurous  acid,  chlorine 
and  the  like,  there  still  remain  in  the  gas  certain  impurities  which  cannot  be  elimi- 
nated by  the  usual  absorption  reagents.  Accordingly  it  is  recommended  to  wash 
the  hydrogen  with  concentrated  sulfuric  acid,  then  to  pass  it  over  solid  caustic 
soda,  which  treatment  is  said  to  remove  the  troublesome  bodies.  To  effect  the 
combination  of  the  unaltered  ethylene  and  hydrogen  in  the  gaseous  mixture  resulting 
from  the  passage  of  these  gases  over  a  catalyst,  the  product  is  again  passed  over 
the  catalyst  under  pressure.  The  reaction  is  stated  to  be  quantitative  and  instan- 
taneous. Nickel  or  a  metal  of  the  platinum  group  may  be  used  as  a  catalyst. 
(German  Patent  265,171,  Oct.  16,  1912.) 

From  a  very  lengthy  paper  published  by  Sabatier  and  Senderens  * 
the  following  items  on  the  preparation  and  use  of  catalyzers  have  been 
noted. 

Access  of  air  to  the  catalyzer  oxidizes  it  and  destroys  or  diminishes 
its  activity.  To  prepare  catalytic  material  one  should  use  an  oxide 
quite  free  of  chlorine  or  sulfur.  Good  results  are  obtained  by  dis- 
solving the  metal  in  pure  nitric  acid  and  forming  the  oxide  by  calcina- 
tion at  a  low  red  heat.  Reduction  of  the  oxide  should  be  with  pure 
hydrogen,  free  from  chlorine  or  sulfur.  Reduction  should  take  place 
at  a  low  temperature,  always  below  a  red  heat,  or  the  catalyzer  will  not 
be  efficient. 

Nickel  reduced  at  a  red  heat  has  practically  no  activity.  At  300°  C. 
it  gives  a  very  active  material  if  used  immediately.  It  is  better,  how- 
ever, to  employ  a  temperature  of  350°  C.  Copper  is  best  treated  at 
300°  C.,  while  cobalt  f  requires  400°  C.  Iron  is  difficult  to  reduce. 
At  450°  C.  some  6  or  7  hours  are  required  to  completely  transform  the 
oxide  into  the  metal.  Nickel  and  copper  are  actually  reduced  near 
200°  C.,  so  even  if  some  oxidation  of  the  catalyzer  were  taking  place, 

*  Ann.  de  Chim.  et  de  Phys.,  1905  (4),  319. 

f  The  reduction  of  cobalt  oxides  by  hydrogen  and  carbon  monoxide  at  different 
temperatures  is  described  by  Kalmus.  (Jour.  Ind.  Eng.  Chem.  (1914),  112-114.) 
For  some  metals  the  minimum  temperature  of  reduction  is  lower  with  carbon  mon- 
oxide than  with  hydrogen  (Fay  and  Seeker,  J.  Am.  Chem.  Soc.,  1903,  641). 


CATALYZERS  113 

because  of  the  presence  of  oxygen  in  the  hydrogen  gas,  immediate 
reduction  would  occur  thereafter. 

The  hydrogen  employed  is  dried  with  sulfuric  acid,  is  then  passed 
through  a  tube  of  Jena  glass  filled  with  copper  turnings  maintained 
at  a  low  red  heat  and  finally  goes  through  a  long  tube  filled  with 
fragments  of  caustic  potash. 

The  catalyzer  should  be  prepared  in  the  tube  in  which  the  material 
to  be  hydrogenated  is  treated.  * 

For  high  temperatures  a  copper  tube  heated  in  a  bath  of  equal  parts 
of  sodium  and  potassium  nitrate  (which  melts  at  225°  C.)  may  be 
used. 

With  regard  to  the  life  of  the  catalytic  material  the  investigators 
state  that  there  are  three  periods  noticeable. 

1.  A  short  period  when  the  catalyzer  is  becoming  accustomed  to 
the  atmosphere  of  hydrogen  and  the  body  to  be  treated. 

2.  A  period  of  normal  activity. 

3.  A  period  of  decline.* 

The  second  or  normal  period  is  generally  very  long,  if  no  trace  of 
bodies  capable  of  altering  the  surface  of  the  metal  is  present.  For 
example,  with  a  nickel  catalyzer  good  results  were  secured  for  one 
month  in  the  transformation  of  benzene  into  cyclohexane.  The 
operation  was  interrupted  each  night  and  resumed  the  next  morning. 
The  slight  oxidation  over  night  did  no  harm  as  the  oxide  was  reduced 
again  the  next  day  at  the  temperature  of  working,  which  was  180°  C. 

If  in  the  hydrogen  there  is  a  trace  of  certain  bodies,  the  action  of  the 
catalyzer  is  rapidly  suppressed.  Even  tiny  traces  of  chlorine,  bromine, 
iodine  or  sulfur  paralyze  the  nickel.  Nickel  obtained  from  oxide 
carrying  a  little  chlorine  is  usually  devoid  of  activity.  Nickel  from 
oxide  containing  a  trace  of  sulfur  is  likewise  inefficient.  The  pres- 
ence in  the  hydrogen  of  even  faint  traces  of  hydrochloric  acid,  hydro- 
gen sulfide  or  selenium  compounds  produces  the  same  disastrous 
effects.  Traces  of  bromine  in  some  phenol  which  was  used  paralyzed 
the  nickel.  The  same  thing  happened  with  benzol  containing  this 
compound. 

Catalyzers  finally  lose  their  efficiency  either  by  traces  of  poisons 
or  by  a  deposit  of  tarry  or  carbonaceous  material  on  the  catalyzer 
particles.  On  dissolving  spent  nickel  in  hydrochloric  acid  a  fetid 
gas  is  evolved  and  brown  carbonaceous  material  is  deposited. 

According  to  Sabatier  and  Senderens  the  operation  should  be  con- 
ducted to  prevent  liquid  coming  into  contact  with  catalyzer.  The 
temperature  limits  practically  are  those  imposed  by  maintaining  the 
*  These  periods  are  similar  to  those  noted  in  the  case  of  ferments. 


114  THE  HYDROGENATION  OF  OILS 

substance  in  a  state  of  vapor.  Too  high  temperatures  sometimes 
cause  decomposition.  Benzene  becomes  cyclohexane  at  tempera- 
tures up  to  240°  C.,  but  at  300°  C.  the  cyclohexane  gives  benzene  and 
methane : 

3  C6H12  =  2  C6H6  +  6  CH4. 

Copper  and  platinum  work  well  in  case  of  ethylene  groups,  but  are 
not  satisfactory  for  hydrogenation  of  the  aromatic  ring.  Nickel  is 
effective  on  the  latter.* 

Some  peculiarities  of  catalytic  nickel  have  been  recorded  by  Sen- 
derens  and  Aboulenc.f  These  investigators  state  that  the  tempera- 
ture at  which  nickel  oxide  is  reduced  by  hydrogen  is  found  to  depend 
on  the  mode  of  preparation  and  treatment  of  the  oxide  used,  there 
being  also  a  considerable  difference  between  the  temperature  at  which 
reduction  commences  and  that  at  which  it  is  complete.  Complete 
reduction  is  not  effected  below  300°  C.,  but  the  mixture  of  metal  and 
oxide  thus  obtained  is  more  active  than  the  metal  prepared  by  total 
reduction  at  a  higher  temperature,  the  activity  of  reduced  nickel  being 
diminished  by  heating  to  a  comparatively  high  temperature,  although, 
at  the  same  time,  its  catalytic  properties  are  rendered  more  permanent. 
Pyrophoric  nickel,  when  heated  in  the  air,  furnishes  an  oxide  which 
is  reducible  at  a  comparatively  low  temperature,  and  reduced  nickel 
of  impaired  activity  may  be  restored,  therefore,  by  oxidizing  it  and 
again  reducing. 

According  to  Moissan  the  protoxide  of  nickel  in  hydrogen  at  230°  to 
240°  C.  blackens  and  reduces,  giving  a  body  pyrophoric  at  ordinary 
temperature.  Muller  states  the  protoxide  of  nickel  at  210°  to  214°  C. 
in  hydrogen  loses  11  to  14  per  cent  of  oxygen,  apparently  giving 
nickelous  oxide  which  corresponds  to  a  loss  of  10.7  per  cent  oxygen. 
At  270°  C.  it  passes  into  the  metallic  state.  For  hydrogenation  the 
anhydrous  or  hydrated  oxide  of  nickel  supported  on  pumice  is  reduced 
at  270  to  280  degrees  (Brunei) ;  280  degrees  (Leroux) ;  255  to  260  de- 
grees (Godchot) ;  245  to  250  degrees  (Darzens) . 

Senderens  and  Aboulenc,  however,  after  a  protracted  investigation, 
recorded  results  which  in  brief  are  as  follows: 

(a)  Anhydrous  nickel  oxide:  This  oxide  becomes  green  a  little 
above  200°  C.  in  presence  of  hydrogen,  but  the  reduction  commences 
only  at  about  300°  C.  and  is  slow  at  330°  C.  It  goes  on  much  faster 

*  Sabatier  has  reviewed  the  subject  of  catalytic  action  in  organic  chemistry,  the 
publication  appearing  as  Vol.  Ill  of  the  Encycl.  de  Science  Chimique  applique  aux 
arts  industriels. 

t  Bull.  Soc.  Chim.  (1912),  n,  641. 


CATALYZERS  115 

at  380°  C.  up  to  two-thirds  the  amount  of  water  which  should  be 
evolved.  There  reduction  stops.  To  get  complete  reduction  the 
temperature  has  to  be  raised  to  420°  C.  The  nickel  obtained  is 
pyrophoric.  It  serves  very  well  for  the  hydrogenation  of  carbon 
monoxide,  carbon  dioxide,  benzene  and  toluene,  but  does  not  work 
well  with  the  phenols. 

(b)  Nickel  oxide  obtained  by  calcination:    This  shows  a  great  re- 
sistance to  reduction.     It  is  necessary  to  raise  the  temperature  to 
420°  C.  to  obtain  two-thirds  of  the  water  of  theory  and  to  a  red  heat 
to  secure  complete  reduction.     Heated  to  this  last-named  temperature 
the  product  is  inactive  even  with  carbon  monoxide  which  is  very  easily 
hydrogenated.     It  is  pyrophoric,  however.     The  efficiency  of  nickel 
as  a  catalyzer  does  not  depend  on  any  pyrophoric  property.     Non- 
pyrophoric  nickel  has  been  prepared  which  is  a  good  catalyzer.     Re- 
duction of  the  oxide  (6)  at  420°  C.  gives  about  one-third  oxide  with 
two-thirds  metal.     This  mixture  is  active  and  pyrophoric.     It  easily 
converts  water  gas  into  methane. 

(c)  Hydrate  of  nickel :  Introducing  hydrate,  prepared  in  the  labora- 
tory, into  the  tube  used  for  reduction,  the  dehydration  was  very  slight 
at  200°  C.,  while  at  230°  C.  reduction  took  place  and  at  270°  C.  de- 
hydration and  reduction  progressed,  but  rather  slowly.     In  another 
experiment  the  same  "  hydrate  "  was  reduced  after  gently  heating  in 
a  crucible  to  remove  the  water.     The  reduction  presented  the  same 
variations  commencing  about  230°  C.  and  progressing  very  gently 
up  to  270°  C.  at  which  point  water  was  given  off  regularly  for  6  hours 
in  an  amount  corresponding  to  one-third  the  total  expected  from  the 
reduction  of  the  oxide.     At  300°  C.  two- thirds  of  the  water  was  col- 
lected and  at  320°  C.  the  remainder  was  obtained  after  treatment  for 
several  hours. 

Another  hydrate  of  nickel  furnished  by  a  chemical  supply  house 
was  more  difficult  to  reduce,  not  giving  off  as  much  water  as  the  pre- 
ceding at  temperatures  20  to  30  degrees  higher. 

Oxides  of  pyrophoric  nickel:  These  may  be  obtained  by  letting 
pyrophoric  nickel  oxidize  in  a  thin  layer  in  the  cold  or  by  heating.  In 
the  cold  the  oxidation  is  variable;  when  heated  the  reaction  is  com- 
plete in  a  moment.  The  oxides  obtained  in  this  manner  commence 
to  reduce  at  a  temperature  much  lower  than  those  from  which  the 
pyrophoric  nickel  was  derived.  For  example,  the  oxide  resulting 
from  the  simple  exposure  to  the  air  of  the  pyrophoric  nickel  obtained 
from  the  hydrate  (c)  was  reduced  at  210°  C.  by  hydrogen,  giving  about 
one-half  the  theoretic  water. 

The  oxide  obtained  by  moderate  calcination  in  the  air  of  this  same 


116  THE  HYDROGENATION  OF  OILS 

pyrophoric  nickel  takes  up  hydrogen  at  250°  C.  giving  off  half  the 
theoretic  water;  after  which,  to  complete  the  reduction  it  is  neces- 
sary to  raise  the  temperature  as  in  the  preceding  case. 

The  anhydrous  oxide  (a)  commenced  to  reduce  at  300°  C.,  reduction 
was  slow  at  330°  C.  and  normal  only  at  380°  to  420°  C.  The  pyro- 
phoric metal  which  results  when  this  material  is  heated  in  contact  with 
air  furnishes  an  oxide  of  which  one-third  is  reduced  at  280°  C.  and 
half  at  320°  C.  The  activity  of  the  nickel  reduced  from  these  oxides 
is  at  least  equal  if  not  superior  to  that  obtained  by  the  reduction 
of  the  normal  oxide. 

When  the  nickel  begins  to  weaken  in  catalytic  effect  it  is  necessary 
only  to  oxidize  and  then  reduce  it,  in  order  to  have  the  catalyzer  com- 
pletely regenerated. 

Passivity  of  nickel  as  a  catalyzer:  If  used  to  hydrogenate  phenol 
for  a  day  or  two  it  will  then  hydrogenate  cresol,  but  if  used  for  a  month 
on  phenol  it  will  not  be  active  on  cresol,  although  still  active  on  phenol. 
By  oxidizing  and  then  reducing,  the  material  is  very  active  on  cresol. 

Anhydrous  oxides  and  hydrates  of  nickel  cannot  be  completely 
reduced  to  the  metal  at  300°  C.,  but  a  mixture  of  the  metal  and  oxide 
results.  It  is  nevertheless  true  that  such  mixtures  are  more  active 
than  if  complete  reduction  with  corresponding  elevation  of  the  tem- 
perature had  taken  place. 

Two  stages  of  oxidation,  derived  from  the  same  pyrophoric  nickel  of 
which  in  one  case  the  reduction  was  arrested  at  250°  C.  when  one-half 
the  oxide  remained,  and  in  the  other  case  the  material  was  heated 
up  progressively  to  350°  C.  to  give  total  reduction,  were  tested.  The 
latter  hydrogenated  xylenol  normally,  while  the  former  gave  a  hydro- 
carbon. To  evade  this  destructive  action  in  a  number  of  cases  the 
investigators  heated  the  nickel  after  reduction  to  a  higher  temperature 
to  diminish  its  activity  and  conserve  its  life  as  a  catalyzer.* 

*  Padoa  and  Fabris  (J.  S.  C.  I.,  1908,  1083)  showed  that  at  ordinary  pressure 
indene  is  not  capable  of  combining  with  hydrogen  in  presence  of  reduced  nickel 
at  300°  C.,  but  that  at  250°  C.  two  atoms  of  hydrogen  are  taken  up.  Ipatiew 
(J.  Russ,  Phys.  Chem.  Soc.  (1913),  45,  994)  finds  that  in  presence  of  nickel  oxide, 
indene  unites  with  hydrogen  at  250°  to  260°  C.  and  110  atmospheres,  yielding  the 
hydrocarbon  octohydroindene.  The  nature  of  the  metal  of  which  IpatiewV  high- 
pressure  apparatus  (J.  S.  C.  I.,  1911,  239)  is  constructed  is  found  to  exert  an  influ- 
ence on  the  hydrogenation,  in  presence  of  cuprous  oxide,  of  compounds  containing 
ethylene  linkages.  Thus,  in  an  iron  tube,  amylene  (trimethylethylene)  is  readily 
converted  into  isopentane,  while  in  a  copper  tube  the  reaction  is  incomplete,  an 
equilibrated  mixture  of  .amylene,  hydrogen  and  isopentane  remaining: 


In  an  iron  tube  and  in  absence  of  cupric  oxide,  no  hydrogenation  occurs.     Similar 


CATALYZERS  117 

Several  types  of  catalyzers  have  been  proposed  for  oil  hardening 
and  in  some  cases  processes  have  been  prescribed  for  operation  with 
specific  catalyzers.  From  the  standpoint  of  the  support  or  carrier  for 
the  primary  active  material  catalyzers  may  be  divided  into  several 
well-defined  groups,  each  exhibiting  characteristic  properties.  The 
classification  embraces : 

CLASSIFICATION  OF  CATALYZERS 

Group  A 
I.   Carrier  porous,  inert  and  coated  but  is  not  impregnated  with 

catalytic  metal. 

II.   Carrier  active,  serving  as  a  secondary  catalyzer  or  feeder,  is 
coated  but  not  impregnated  with  catalytic  metal. 

Group  B 

I.   Carrier  non-porous,  inert  and  is  fairly  evenly  coated  with  cata- 
lytic metal. 

II.   Carrier   non-porous,   inert   and   instead   of   being   coated   is 
punctated  with  metal  nodules. 

III.  Carrier  non-porous,  active  and  is  fairly  evenly  coated  with 

catalytic  metal. 

IV.  Carrier  non-porous,  active,  serving  as  a  secondary  catalyzer 

or  feeder  and  instead  of  being  evenly  coated  is  punctated 
with  metal  nodules. 

Group  C 

I.   Carrier  porous,  inert  and  is  impregnated  with  catalytic  metal. 
II.    Carrier  porous,  active,  serving  as  a  secondary  catalyzer  and 

is  impregnated  with  catalytic  metal. 

Other  subdivisions  follow  if  the  catalytic  material  is  used  in  a 
coarse  condition  or  in  a  finely-divided  state,  etc.  Superficially  treated 
or  coated  carriers  are  regarded  as  more  desirable  for  treating  liquids, 
while  the  porous  impregnated  varieties  find  a  better  field  of  utility  in 
the  hydrogenation  of  gases  or  vapors  which  in  admixture  with  hydrogen 
are  capable  of  penetrating  porous  bodies  into  which  viscous  liquid 
compounds  would  not  readily  diffuse. 

results  are  obtained  with  hydro-aromatic  compounds.  Further,  hydrogenation  in 
an  apparatus  of  phosphor  bronze  in  presence  of  reduced  copper  results  in  the  estab- 
lishment of  an  equilibrium,  while,  if  iron  turnings  are  also  present,  hydrogenation 
proceeds  to  an  end.  The  slight  catalytic  activity  of  reduced  copper  in  copper  tubes 
may  be  regarded  as  due  to  poisoning  of  the  catalyst;  or  the  use  of  cupric  oxide  in 
iron  tubes  may  result  in  a  conjugated  catalytic  action. 

Ipatiew  (Chem.  Centralbl.  (1906),  II,  87)  found  alumina  to  act  aa  a  dehydro- 
genating  catalyzer  on  various  bodies. 


CHAPTER  V 
THE  BASE  METALS  AS   CATALYZERS 

NICKEL  CATALYZERS  —  Continued 

Nickel  oxide  catalyzer  is  recommended  by  Bedford  and  Erdmann* 
as  preferable  to  the  metallic  forms  and  some  of  the  features  claimed  for 
this  material  are  noted  in  the  following:  They  indicate  that  the  hy- 
drogenation of  oils  by  means  of  finely-divided  nickel,  although  now 
worked  on  a  commercial  scale,  has  the  disadvantage  that  the  catalyst 


FIG.  41.  —  Photo-micrograph  of  a  particle  of  crushed  glass  coated  with  nickel  oxide 
(equivalent  to  10  per  cent  of  metallic  nickel). 

is  extremely  sensitive  to  small  quantities  of  air  and  to  traces  of  chlorine 
and  sulfur  compounds,  which  latter  may  be  developed  from  protein, 
always  present  in  vegetable  and  animal  oils.  Oxides  of  nickel  are 
capable  of  acting  as  hydrogen  carriers  for  the  hydrogenation  of  oils  at 
atmospheric  pressure,  and  possess  the  advantage  over  metallic  nickel 
of  being  relatively  insensitive  to  gases  containing  oxygen  and  sulfur 
compounds;  moreover  hydrogenation  proceeds  with  much  greater 
velocity  than  with  metallic  nickel.  Any  one  of  the  oxides  of  nickel 
may  be  used,  viz.,  nickel  sesquioxide,  nickel  monoxide  or  nickel  sub- 

*  J.  Prakt.  Chem.  (1913),  87,  425. 
118 


THE  BASE  METALS  AS  CATALYZERS 


119 


oxide;*  with  the  sesquioxide  and  monoxide  a  temperature  of  about 
250°  C.  is  required,  but  with  nickel  suboxide  180°  to  200°  C.  is  suffi- 
cient. When  the  higher  oxides  of  nickel  are  used  they  become  partially 
reduced  to  the  suboxide  which  is  said  to  form  a  colloidal  suspension  in 
the  oil.  Hence  a  nickel  oxide  catalyst  becomes  more  active  after  it 
has  been  used,  owing  to  the  formation  of  the  suboxide.  No  reduction 
to  metallic  nickel  occurs  during 
the  hydrogenation  process,  al- 
though in  absence  of  oil,  reduc- 
tion of  nickel  oxides  to  metallic 
aickel  by  hydrogen  takes  place 
it  190°  C.  Nickel  suboxide  may 
be  distinguished  from  metallic 
lickel  by  its  lack  of  electric  con- 
luctivity  and  by  its  inability 
;o  form  nickel  carbonyl  when 
created  with  carbon  monoxide 
mder  pressure  at  a  moderate 
.emperature.  Other  metallic  ox- 
des  (e.g.,  copper  oxide,  ferrous 
3xide)  are  also  capable  of  acting 
is  catalyzers  in  the  hydrogen- 
ition  of  oils,  but  do  not  act  so 
well  as  nickel  oxide.  The  activ- 
ity of  nickel  oxide  is  increased  by  small  quantities  of  the  oxides  of 
aluminium,  silver,  zirconium,  titanium,  cerium,  lanthanum  and  mag- 
nesium. Nickel  salts  of  organic  acids  do  not  act  as  catalysts, 
but  in  presence  of  the  heated  oil  are  decomposed  by  hydrogen, 
yielding  nickel  oxides  and,  under  certain  conditions,  also  metallic 
nickel;  the  resultant  nickel  material  then  acts  as  a  catalyst.  Nickel 
formate  in  the  presence  of  the  heated  oil  is  reduced  by  hydrogen  to 
nickel  suboxide  at  210°  C.,  while  at  250°  C.  metallic  nickel  is  also 
produced.  In  carrying  out  the  hydrogenation,  the  oil  is  placed  in  a 
cylindrical  copper  vessel  fitted  with  an  agitator,  and  heated  in  an  oil 
bath  to  180°  C.  while  a  slow  current  of  hydrogen  is  passed  through.  A 
small  quantity  of  nickel  oxide  is  then  added,  the  temperature  is  raised 
to  255°  to  260°  C.,  a  further  addition  of  the  catalyst  is  made  and  the 
supply  of  hydrogen  is  increased.  The  hydrogenation  is  controlled  by 
examining  test-samples  of  the  oil  as  to  melting  point  and  iodine  value. 
The  oil  becomes  black  possibly  owing  to  the  formation  of  "  col- 


FIG.  42.  —  Photo-micrograph  of  a  particle 
of  crushed  glass  coated  with  10  per  cent 
of  reduced  nickel. 


*  Compare  Moore,  Chem.  News  (1895),  7182.     Bohm  (Seifen.  Ztg.  (1912),  1044) 
briefly  discusses  oxide  catalyzers.     See  also  Soap  Gazette  and  Perfumer,  1913,  107. 


120  THE  HYDROGENATION  OF  OILS 

loidal "  nickel  suboxide,  which  passes  through  a  filter-paper,  but  can 
be  removed  by  centrifuging.  Nickel  soaps  are  formed  only  to  a  slight 
extent,  and  probably  in  consequence  of  a  secondary  reaction  during 
the  cooling.  The  hydrogenized  fat  is  free  from  hydroxy-acids.  The 
catalyst  after  use  contains  some  organic  matter  apparently  composed 
partly  of  nickel  palmitate  or  stearate,  and  other  substances,  one  of 
which  probably  is  nickel  carbide.  The  process  is  easy  to  control  if 
pure  hydrogen  is  available,  and  in  an  experimental  plant  of  1  ton 
capacity  Bedford  and  Erdmann  report  that  more  than  100  tons  of 
different  oils  have  been  hardened  by  hydrogenation  in  the  manner 
described. 

Nickel  oxide  catalyzers  have  been  made  the  subject  of  a  number  of 
patents. 

English  Patent  4702,  of  1912,  to  Boberg  and  the  Techno-Chemical 
Laboratories,  Ltd.,  London,  proposes  to  prepare  catalyzer  through  the 
reduction  of  a  metallic  compound  such,  for  example,  as  ignited  nickel 
carbonate,  the  reduction  taking  place  with  hydrogen  under  such  con- 
ditions that  the  nickel  contains  one  or  more  suboxides,  or  when  nickel 
is  employed  a  compound  is  formed  which  contains  less  oxygen  than 
the  ordinary  oxide  NiO.* 

The  observation  is  made  that  in  the  reduction  of  ignited  nickel  car- 
bonate by  hydrogen  the  product  obtained  is  just  so  much  more  effi- 
cient catalytically  the  lower  the  temperature  at  which  the  reduction 
takes  place,  because  of  the  suboxide  formed.  The  catalyzer  apparently 
also  contains  some  hydrogen.  The  preparation  of  the  catalyzer  is 
carried  out  by  passing  ignited  nickel  carbonate,  free  from  injurious 
impurities,  continuously  in  a  slow  stream  through  an  inclined  rotary 
cylinder,  which  is  heated  in  part  or  throughout  its  length,  while  hydro- 
gen is  allowed  to  flow  through  in  an  opposite  direction.  By  suitable 
regulation  of  the  influx  of  the  material  as  well  as  the  proper  regulation 
of  the  temperature,  the  reduction  may  be  carried  out  in  such  a  manner 
that  one  obtains  a  catalyzer  which  is  partly  or  mainly  composed  of  the 
suboxide.  The  most  suitable  temperature  is  between  230°  to  270°  C. 
and  the  length  of  the  heating  operation  must  be  just  so  much  more 
prolonged  the  lower  the  maintained  temperature.  Unnecessarily 
long  heating  must  be  avoided  otherwise  the  reduction  goes  too  far 
which  causes  a  diminution  in  catalytic  activity.  The  catalyzer  so 
obtained  can  be  used  immediately  for  oil  hardening  or  it  may  be  pre- 

*  The  proposal  by  Boberg  to  prepare  a  catalyzer  from  nickel  carbonate  by  ignition 
and  reduction  to  form  a  mixture  of  nickel  and  its  suboxide  is  criticized  by  the  editor 
of  the  Chemiker  Zeitung  (Chem.  Ztg.  (1913),  481)  as  offering  nothing  novel  in  view 
of  Bedford's  disclosures  in  English  Patent  29,612,  1910. 


THE  BASE  METALS  AS  CATALYZERS  121 

served  in  contact  with  air  where  it  oxidizes  very  slowly,  provided  local 
over-heating  is  avoided. 

One  can  also  collect  the  catalyzer  in  water,  filter  and  dry  in  the  air; 
or  it  can  be  collected  in  an  atmosphere  of  hydrogen  which  is  gradually 
displaced  by  air. 

The  production  of  suboxide  catalysts  is  also  carried  out  by  reducing 
nickel  oxide  as  completely  as  possible  and  then  controllably  oxidizing 
the  product  in  any  suitable  way  as  with  air  or  oxygen  diluted  with  an 
indifferent  gas,  such  as  carbon  dioxide,  so  that  the  introduction  of 
oxygen  can  progress  without  local  overheating.  Such  oxidation  can 
go  on  between  300°  to  600°  C. 

The  degree  of  catalytic  activity  of  a  metal  oxide  depends  not  only 
on  its  chemical  but  also  on  its  physical  properties.  It  is  known  that 
metal  catalyzers,  such  as  nickel,  cobalt  and  iron,  require  very  fine 
division  for  effective  action.  The  same  is  also  true  of  the  oxides  of 
these  metals.  The  German  Patent  to  Erdmann  and  Bedford  (260,009, 
1911)  relates  to  oxide  catalyzers  in  a  voluminous  form.  The  patentees 
state  that  metal  oxides  may  be  obtained  in  the  form  of  an  especially 
finely-divided  voluminous  material  if  one  takes  a  concentrated  aqueous 
solution  of  the  nitric  acid  salt  from  which  the  oxide  is  to  be  made, 
mixes  with  it  a  water-soluble  organic  compound  rich  in  carbon  and 
then  subjects  the  mixture  to  combustion  by  allowing  it  to  fall,  drop 
by  drop;  into  a  heated  vessel.  The  strong  evolution  of  gas  which  thus 
takes  place,  due  to  the  combustion  of  the  organic  compound  and 
simultaneous  decomposition  of  the  nitrate,  produces  nickel  oxide  in  a 
very  voluminous  form.  Especially  recommended  for  this  purpose  are 
the  sugars  and  carbohydrates,  for  these  when  heated  by  themselves 
produce  a  strongly-swelling  carbonaceous  mass.* 

As  an  example  Erdmann  and  Bedford  state  that  nitric  acid  of  1.42 
specific  gravity  is  diluted  with  an  equal  volume  of  water.  Pure  metal- 
lic nickel  is  introduced.  After  the  reaction  is  complete  the  solution  is 
heated  for  two  hours  with  an  excess  of  nickel  in  order  to  completely 
neutralize  the  nitric  acid  and  to  separate  any  iron  present  as  a  pre- 
cipitate of  iron  hydroxide.  The  clarified  nickel  nitrate  solution  is 
evaporated  to  specific  gravity  of  1.6  and  to  one  liter  of  this  fluid,  cor- 
responding to  250  grams  of  nickel,  180  grams  of  powdered  cane  sugar 
are  introduced.  This  solution  is  allowed  to  run  in  portions  into  a 
muffle  heated  to  a  low  red  heat.  Each  portion  is  heated  until  no 

*  The  use  of  sugar  or  gum  in  a  somewhat  similar  manner  has  been  described  by 
Schroeder  (J.  S.  C.  I.,  1902,  344  and  British  Patent  10,412,  1901),  who  found  it 
possible  to  increase  the  porosity  of  catalytic  material  by  ignition  with  such  carbo- 
naceous matter,  so  as  to  form  blowholes  or  bubbles  in  the  catalytic  mass. 


122  THE  HYDROGENATION  OF  OILS 

more  red  vapors  depart,  when  the  voluminous  nickel  oxide  which  is 
formed  is  removed  from  the  muffle  and  a  fresh  portion  of  the  solution 
is  introduced. 

In  place  of  cane  sugar  other  varieties  of  sugar  may  be  applied  and 
also  water-soluble  starch,  dextrine,  gum,  tartaric  acid  or  other  water- 
soluble  organic  acid  substances  which  are  rich  in  carbon. 

In  a  similar  manner  the  oxides  of  cobalt  and  iron  or  other  cata- 
lytically-active  oxides  may  be  brought  into  a  voluminous  form.* 

It  is  the  belief  of  Erdmann  f  that  the  oxide  catalysts  are  superior 
to  metal  catalytic  material,  because  the  former  not  only  have  strongly 
marked  catalytic  properties  but  they  are  more  stable  than  the  latter. 
Erdmann  refers  to  prior  investigations  of  Ipatiew  who  worked  with 
various  organic  compounds  other  than  fats,  employing  nickel  oxide 
and  hydrogen  under  very  high  pressure;  while  in  the  present  case 
fatty  material,  it  is  claimed  by  Erdmann,  is  smoothly  hydrogenated 
under  ordinary  atmospheric  pressure.  For  example,  linseed  oil  or 
any  other  fatty  oil  may  be  heated  with  one-half  to  one  per  cent  of 
nickel  oxide,  such,  for  example,  as  may  be  obtained  by  calcining  pure 
nickel  nitrate  at  a  low  red  heat.  The  temperature  of  the  linseed  oil 
is  raised  to  about  255  degrees  and  a  stream  of  hydrogen  is  passed 
through  the  oil  when  it  is  observed  that  the  nickel  oxide  and  oil  mix- 
ture becomes  deep  black  and  the  oxide  appears  to  undergo  subdivision 
and  possibly  transformation  into  a  colloidal  state,  the  solvent  acquiring 
an  ink-like  appearance.  At  the  same  time  hydrogen  is  absorbed  and 
the  oil  is  hydrogenated. 

This  "colloidal  "  form  of  nickel  oxide  catalyzer,  which  apparently  has 
not  been  observed  with  metallic  nickel,  is  regarded  by  Erdmann  as 
of  great  importance  in  this  art  because  it  enables  a  finely-divided 
catalyzer  of  an  effective  nature  to  be  so  easily  prepared.  When  the 
hardening  process  is  finished  the  nickel  oxide  catalyzer  clots  and 
collects  so  that  it  may  be  separated  readily  from  the  hardened  fat. 

The  analyses  of  the  hardened  products  of  linseed,  peanut  and  sesame 
oil  show  that  by  the  process  an  approximately  pure  glyceride  of  stearic 
acid  is  produced  without  any  trace  of  oxy  fatty  acid  impurity. 

Nickel  soaps  form  in  the  presence  of  free  fatty  acid  only  in  an  in- 
consequential way  to  an  amount  of  about  TJT  of  1  per  cent  or  so. 
This  slight  amount  is  said  to  remain  along  with  the  catalyzer  in  an 
undissolved  state. 

*  Siiboxide  of  nickel  is  prepared  for  catalytic  purposes,  according  to  Bedford 
and  Williams  (J.  S.  C.  I.,  1914,  324),  by  heating  a  mixture  of  nickel  oxide  or  an 
organic  salt  of  nickel  with  oil  in  a  current  of  hydrogen. 

t  Seifen.  Ztg.  (1913),  605. 


THE  BASE  METALS  AS  CATALYZERS  123 

The  whole  hardening  process,  when  pure  hydrogen  is  at  one's  dis- 
posal, is  so  simple  with  reference  to  the  apparatus  required,  and 
operates  so  smoothly  that  the  shifting  from  the  laboratory  experiments 
to  work  on  a  large  scale  is  stated  to  have  offered  no  difficulties. 

In  one  experiment  carried  out  by  Bedford  and  Erdmann  *  3  grams  of  freshly  pre- 
pared nickel  oxide  were  added  to  30  grams  of  cottonseed  oil  and  treated  with  hydro- 
gen at  260°  C.  until  the  oxide  had  become  black  in  color  and  very  finely  divided. 
The  solidifying  point  of  the  fat  was  then  48°  C.  The  mixture  was  cooled  to  185°  C., 
270  cc.  of  cottonseed  oil  added  and  a  strong  current  of  hydrogen  passed  through  the 
oil  and  catalyzer  (maintained  at  185°  C.),  for  one  hour  when  the  solidifying  point 
was  found  to  be  45°  C. 

Another  interesting  question  to  which  reference  has  already  been 
made  is  whether  or  not  nickel  oxide  in  oil  is  reduced  to  metallic  nickel 
by  hydrogen,  and  whether  any  finely-divided  metal  which  might  arise 
in  this  manner  is  a  carrier  of  hydrogen.f 

While  nickel  oxide  (NiO  or  N2O)  yields  nickel  in  an  hydrogen  atmos- 
phere at  260  degrees  and  even  in  fact  as  low  as  190  degrees,  the  be- 
havior of  these  bodies,  according  to  Erdmann,  is  very  different  when 
they  are  immersed  in  oil.  In  the  latter  case  the  oil  acts  as  a  protective 
element  and  hinders  or  prevents  complete  reduction.  The  reduction 
goes  no  further  than  the  suboxide  stage,  and  Erdmann  believes  that 
some  sort  of  an  addition  compound  is  formed  with  the  unsaturated  oil. 
If  the  catalyzer  is  removed  from  the  hardened  fat  and  entirely  freed 
from  the  latter  by  extraction  with  benzol,  the  used  catalytic  material 
is  obtained  in  the  form  of  a  soft  black  powder  which  is  more  or  less 
strongly  magnetic,  but  which  does  not  possess  any  conducting  power 
for  electricity. 

A  great  number  of  analyses  have  shown  that  the  nickel  content 
lies  between  nickelous  oxide  and  a  form  of  suboxide  described  by 
Moore. |  Not  the  slightest  trace  of  metallic  nickel  is  found  in  the 
used  catalyzer  if  the  fatty  oil  is  free  from  strongly  reducing  substances 
such  as  aldehydes  or  formic  acid. 

*  Jour.  f.  prakt.  Chem.,  1913,  446. 

t  The  possibility  of  nickel  oxide  and  carbonate  becoming  reduced  during  hydro- 
genation  operation,  so  as  to  actually  yield  a  metallic  catalyzer  similar  to  that  cov- 
ered by  the  Leprince  and  Siveke  basic  patent,  is  considered  by  Mayer  (Seifen.  Ztg. 
(1913),  1224)  who  also  discusses  the  situation  in  Germany  respecting  patented 
processes  of  hydrogenation. 

Professor  Erdmann  (Seifen.  Ztg.  (1913),  1325)  discusses  the  scope  of  the  Le- 
prince and  Siveke  German  Patent  141,029  corresponding  to  the  Normann  British 
Patent  1515,  1903,  especially  with  regard  to  the  use  of  nickel  oxide  catalyzer  in  the 
form  employed  by  Bedford  and  Erdmann. 

t  Chem/News,  71,  82. 


124  THE  HYDROGENATION  OF  OILS 

The  absence  of  metallic  nickel*  is  rather  definitely  shown  through 
the  indifferent  electrical  conductivity  of  some  used  nickel  oxide  cata- 
lyzer from  which  the  fat  had  been  removed,  the  oxide  being  pressed 
into  block  form  for  the  purposes  of  such  test.  A  control  test  made 
with  catalyzer  which  before  use  had  received  an  addition  of  a  few 
per  cent  of  freshly-reduced  nickel  showed,  under  like  circumstances, 
a  relatively  high  electrical  conductivity.  Also  the  very  different  be- 
havior of  carbon  monoxide  toward  metallic  nickel  and  nickel  oxide 
indicates  the  non-metallic  nature  of  the  used  nickel  oxide  catalyzer. 

So  in  two  ways  it  is  alleged  to  have  been  shown  that  under  normal 
conditions  of  the  process  of  hydrogenation,  nickel  oxide  is  not  reduced 
to  metallic  nickel.  According  to  Erdmann,  after  numerous  compara- 
tive tests,  a  great  advantage  of  the  process  over  those  made  known 
up  to  this  time  has  been  established.  The  fact  that  nickel  oxide  cata- 
lyzers experience  a  partial  reduction  to  nickel  suboxide  brings  up  the 
question  as  to  whether  or  not  the  suboxide  is  the  only  oxide  of  nickel 
which  is  capable  of  transferring  hydrogen  to  unsaturated  compounds. 

In  the  application  of  the  higher  oxide  the  first  phase  of  the  hydro- 
genation which  takes  place  at  250  degrees  is  that  of  the  formation  of 
magnetic  suboxide,  and  the  once-used  nickel  oxide  catalyzer  possesses 
more  marked  activity  than  the  unused.  With  such  a  once-used 
catalyzer  hydrogenation  progresses  with  much  greater  rapidity  and 
also  at  an  essentially  lower  temperature.  After  use  eight  times  the 
nickel  oxide  catalyzer  was  still  active. 

Erdmann  prepared  Moore's  suboxide  through  electrical  reduction 
from  a  solution  of  nickel  potassium  cyanide.  This  he  found  possessed 
the  properties  stated  by  Moore,  namely,  it  was  magnetic,  reduced 
nitric  acid,  developed  hydrogen  with  mineral  acids  and  showed  no 
electrical  conductivity.  The  compound,  both  in  water  and  in  oil, 
showed  colloidal  properties.  When  introduced  into  hot  cottonseed  oil 
it  distributed  itself  through  the  oil  in  the  form  of  a  very  fine  suspen- 
sion which  colored  the  oil  black,  and  treatment  with  hydrogen  at 
210°  C.  indicated  that  the  compound  even  at  that  relatively  low  tem- 
perature was  an  excellent  reduction  catalyzer. 

In  passing,  it  may  be  mentioned  that  other  oxides  besides  nickel 
have  been  found  to  possess  the  property  of  transferring  hydrogen. 

*  Meigen  and  Bartels  (J.  prakt.  Chem.,  1914,  301)  consider  the  views  of  Erdmann, 
regarding  the  formation  of  nickel  suboxide  when  employing  an  oxide  catalyzer,  to 
be  untenable,  and  conclude  that  metallic  nickel  is  formed  under  the  conditions 
established  by  hydrogenation.  Experimental  studies  in  support  of  this  position 
are  detailed.  From  the  analytical  results,  the  electrical  conductivity  and  the 
observed  formation  of  nickel  carbonyl,  Meigen  and  Bartels  consider  metallic  nickel 
to  be  indicated,  contrary  to  the  views  of  Erdmann. 


THE  BASE  METALS  AS  CATALYZERS  125 

This  has  been  noted  with  copper  and  iron  oxide.  Osmium  tetroxide 
has  been  found  by  Lehmann  to  effect  hydrogenation  while  in  itself 
becoming  converted  into  colloidal  osmium  dioxide. 

A  comparison  has  been  made  by  Erdmann  between  oxide  catalyzers 
and  organic-salt  catalyzers,  such  as  the  formate,  acetate,  oleate  and 
other  similar  salts  which  have  been  studied  in  connection  with  oil 
hardening,  and  Erdmann  has  reached  the  conclusion  that  these  salts 
do  not  act  directly  as  catalyzers.  In  order  to  effect  hardening  it  is 
necessary  to  break  down  the  organic  salt.  It  does  not  in  itself  possess 
the  property  of  acting  as  a  hydrogen  carrier.  So  long  as  it  remains 
unchanged  no  hydrogenation  takes  place.  As  soon,  however,  as  a 
sufficiently  high  temperature  is  reached,  Erdmann  thinks  these  organic 
nickel  salts,  under  the  influence  of  hydrogen,  are  decomposed  in  such 
a  way  as  to  form  nickel  oxide  and  the  suboxide,  which  latter  possesses 
the  property  of  forming  an  oil  colloid  and  becomes  active  as  a  catalyst. 

Under  some  circumstances  a  mirror  of  metallic  nickel  forms  on  the 
walls  of  the  vessel;  this  occurs  especially  easily  when  nickel  oleate  is 
used,  and  also  has  been  noted  with  nickel  formate  when  the  oil  is 
maintained  at  a  relatively  high  temperature,  approximately  250°  C. 
The  metallic  nickel  which  forms  as  a  mirror  or  otherwise,  it  is  claimed, 
does  not  exert  a  catalytic  action,  but  the  nickel  oxides  which  arise 
and  which  pass  into  the  oil  in  a  finely-divided  condition  are  effective 
catalysts.* 

The  application  of  organic  nickel  salts,  such  as  nickel  formate,  suffers 
the  disadvantage  that  the  action  is  not  immediate,  because  time  is 
required  to  effect  the  decomposition  of  the  formate.  Furthermore, 
there  is  the  loss  in  formic  acid  and  the  costliness  of  regenerating  the 
catalyzer.* 

*  Bohm  (Seifen.  Ztg.  (1912),  737,  Soap  Gazette  and  Perfumer,  1913, 107)  advances 
the  rather  sweeping  view  that  many  of  the  patents  issued  subsequent  to  the  Leprince 
and  Siveke  German  Patent  141,029,  1902,  have  little  or  no  standing.  He  states 
that  operations  involving  changes  in  air  pressure  are  common  expedients  of  organic 
chemistry;  that  spraying  oils  to  secure  intimate  contact  with  gases  is  well  known, 
citing  such  use  in  the  linseed  oil  industry;  and  that  metallic  catalyzers  in  the  col- 
loidal form  may  fall  within  the  definition  of  a  finely-divided  metal.  He,  however, 
regards  the  metal  salt  catalyzers  as  being  independent  of  the  Leprince  and  Siveke 
Patent,  but  expresses  some  doubt  as  to  the  continuance  of  their  use  in  Germany  after 
the  expiration  in  1917  of  German  Patent  141,029. 

The  views  of  Bohm  are  criticized  in  the-  Seifensieder  Zeitung  (1912),  1001,  his 
idea  that  almost  all  patents  for  oil  hardening  will  lose  their  value  with  the  expiration 
of  the  Leprince  and  Siveke  Patent  in  1917  being  regarded  as  erroneous.  The 
contrary  is  more  likely  to  take  place,  that  is,  the  value  of  these  processes  will  advance. 
It  is  a  matter  of  surprise  that  Bohm  regards  the  metal  salt  catalyzers  as  independent 
of  the  Leprince  and  Siveke  Patent.  Nickel  formate,  as  well  as  other  salts,  such  as 


126  THE  HYDROGENATION  OF  OILS 

Sabatier  and  Espil  have  studied  the  reduction  by  hydrogen  of  nickel 
oxide  obtained  by  igniting  the  nitrate.  Reduction  takes  place  at 
170°  C.,  at  which  temperature,  after  112  hours,  72  per  cent  were  re- 
duced. Thereafter  the  reaction  progressed  more  slowly  and  after  160 
hours  the  conversion  amounted  only  to  80  per  cent.  These  and  other 
observations  appear  to  disprove  the  claim  made  by  Glaser  that  below 
330°  C.  not  over  50  per  cent  of  nickel  are  reduced  and  that  the  oxide 
Ni2O  is  produced.  In  fact,  the  work  of  Sabatier  and  Espil  would  in- 
dicate the  existence  of  a  difficultly  oxidizable  oxide  having  the  formula 
Ni40.* 

Sabatier  and  Espil  in  a  further  investigation  of  the  question  of 
degree  of  reduction  of  nickel  oxide  when  heated  in  the  presence  of 
hydrogen  make  note  f  that  a  careful  calcination  of  nickel  nitrate 
affords  nickel  oxide  which  reduces  to  metallic  nickel  at  a  temperature 
of  155°  C.  without  the  production  of  a  non-reducible  suboxide. 
When  the  oxide  is  calcined  at  a  bright  red  heat  reduction  takes  place 
at  155°  C.,  but  the  action  is  slower. 

An  additional  contribution  to  this  subject  by  Sabatier  and  Espil 
(Comp.  rend.  1914,  668)  indicates  that  sufficient  metallic  nickel  is 
formed  from  the  oxide  in  oil  to  explain  the  catalysis  observed  in  the 
case  of  the  Bedford-Erdmann  process.  Sabatier  and  Espil  use  the  term 
coefficient  of  reduction  to  represent  the  proportion  of  oxide  reduced  per 
hundred  parts.  At  240°  C.  on  three  hours  exposure  to  hydrogen,  an 
oxide  of  nickel  which  had  been  prepared  by  calcination  at  550°  C. 

nickel  lactate,  acetate,  etc.,  proposed  by  Wimmer  and  Higgins,  are  first  broken 
down  into  nickel  oxide  and  acid;  while  under  the  influence  of  heat  and  hydrogen 
the  organic  acid  is  further  decomposed  and  the  nickel  oxide,  at  least  in  part,  appar- 
ently is  reduced  to  metallic  nickel.  Without  the  presence  of  metallic  nickel  hydro- 
genation  is  thought  to  be  scarcely  possible. 

The  decomposition  of  nickel  formate  into  acid  and  metallic  nickel  is  said  to  be 
very  easily  demonstrated  by  a  laboratory  test.  Wimmer  and  Higgins  may  perhaps 
conduct  the  process  so  as  not  to  form  metallic  nickel.  A  serious  disadvantage  exists 
in  the  regeneration  of  the  once-used  contact  material  of  this  character;  for  recon- 
version into  nickel  formate,  acetate  and  other  costly  organic  salts  is  an  expensive 
operation.  The  oxide  catalyzers  likewise  would  be  expected  to  form  metallic  nickel 
during  the  hydrogenation  process,  even  though  the  reduction  be  only  partial.  From 
the  work  of  Ipatiew  such  reduction  apparently  does  not  take  place.  Possibly  the 
envelopment  of  the  molecules  of  oxide  by  oil  hinders  the  reducing  action  of  the 
hydrogen. 

The  doubts  formerly  had  with  regard  to  the  effectiveness  of  oxide  catalysts  have 
now  vanished,  for  during  a  considerable  period  this  contact  material  has  been  used 
for  hardening  oils  on  the  large  scale.  A  reduction  of  the  oxides  to  the  metallic 
state  has  not  been  observed  under  these  circumstances. 

*  Chem.  Ztg.  (1913),  1121. 

t  Chem.  Ztg.  (1913),  1549. 


THE  BASE  METALS  AS  CATALYZERS  127 

showed  a  coefficient  of  reduction  of  93,  while  oxide  which  had  been 
ignited  at  a  bright  red  heat  exhibited  a  coefficient  of  32.8.  (These 
figures  relate  to  the  dry  oxide  not  in  oil.)  At  155°  C.  on  96  hours  ex- 
posure to  hydrogen,  a  light  oxide  gave  a  reduction  coefficient  of  56  and 
a  calcined  oxide  was  found  to  have  a  coefficient  of  only  2.5.  The  rate 
of  reduction  was  found  to  be  somewhat  accelerated  by  increase  in  the 
rate  of  flow  of  hydrogen  over  the  oxide  mass.  At  240°  C.,  with  a  rate 
of  flow  of  hydrogen  of  6  cu.  cm.  per  minute  the  coefficient  was  44.5,  at 
17  cu.  cm.  the  coefficient  increased  to  65  and  at  24  cu.  cm.  the  coefficient 
became  77.5.  Sabatier  and  Espil  note  that  elevation  of  the  temperature 
greatly  increases  the  speed  of  reduction.  At  220°  C.  with  oxide  of 
nickel,  the  following  coefficients  were  obtained. 

1  hour 14.9 

4  hours 57.6 

5.5  hours 77.4 

6.5  hours 78.0 

7 . 5  hours 79 . 9 

22  hours 99.6 

At  250°  C.  the  coefficients  were  found  to  be  as  follows: 

J  hour 30 . 0 

1  hour 52 . 0 

1 . 5  hours 78 . 9 

2  hours 87 . 0 

2.5  hours 92.5 

3  hours 95 . 3 

15  hours 100 . 0 

Between  190°  to  240°  C.  the  speed  of  reduction  is  an  exponential  func- 
tion of  the  temperature.  The  reduction  of  nickel  oxide  at  175°  C. 
gave  a  coefficient  of  10  and  on  treating  this  product  with  carbon  mon- 
oxide at  50°  C.  nickel  carbonyl  was  obtained.  Sabatier  and  Espil  con- 
clude that  a  suboxide  is  formed  by  reduction  in  this  manner,  having 
the  composition  Ni40,  corresponding  to  the  coefficient  75.  This  sub- 
oxide  is  not,  however,  irreducible  but  is,  as  stated  above,  more  slowly 
reduced  than  the  protoxide. 

Dry  hydrogen  has  been  found  to  reduce  the  oxide  better  than  moist 
gas  and  in  practice  it  is  recommended  that  the  hydrogen  employed  for 
reduction  purposes  be  freed  from  moisture  before  use.* 

t  Sabatier  and  Espil  have  observed  that  moist  hydrogen  is  at  least  as  active  as 
dry  hydrogen  in  the  hydrogenation  of  benzene  and  phenol  (Bull.  Soc.  Chim.,  1914, 

228). 


128 


THE  HYDROGENATION  OF  OILS 


The  rate  of  hardening  of  cottonseed  oil  by  nickel  and  nickel  oxide 
catalyzers  has  been  investigated  by  Meigen  and  Bartels  (J.  prakt. 
Chem.,  1914,  293)  and  their  results  are  shown  in  Fig.  43.  Curves  1,  2 
and  3  were  derived  with  metallic  nickel  at  170°  C.,  and  4  and  5  with 
nickel  oxide  at  250°  to  255°  C.  The  amount  of  catalyzer  in  all  cases 
corresponded  to  two  per  cent  of  nickel  oxide.  No.  1  was  obtained  with 
nickel  prepared  from  the  carbonate,  No.  2  from  reduced  oxide  and  No. 
3  from  a  commercially-used  catalyzer.  The  oxide  employed  in  Nos.  4 
and  5  was  obtained  by  ignition  of  the  nitrate.  These  curves  indicate 
a  slower  action  for  the  oxide,  which  Meigen  and  Bartels  attribute  to  the 
time  required  for  preliminary  reduction  of  the  oxide  after  its  addition 
to  the  oil,  and  before  actual  hydrogenation  of  the  oil  occurs. 

Free  oleic  acid  can  be  hardened  very  easily  by  means  of  a  nickel 
oxide  catalyzer,  according  to  Bedford  and  Erdmann*  Nickel  oleate 
forms  only  in  slight  amount. 

Pure  nickel,  obtained  by  reduction  of  the  nitrate,  according  to 
Chem.  Fabr.  auf  Actien,f  is  inactive  for  the  purpose  of  converting 

borneol  into  camphor;  if,  however,  a 
small  quantity  of  sodium  carbonate 
be  added  to  the  nitrate  before  re- 
duction, a  very  active  product  is 
obtained;  a  similar  mixture  is  ob- 
tained by  adding  0.17  per  cent  of 
pure  sodium  oxide  to  .the  nickel; 
other  bases  or  salts  which  are  not 
readily  reduced  at  a  red  heat  may 
be  used  in  place  of  sodium  oxide. 
Further,  if  a  small  quantity  of  cer- 
tain other  metals  is  introduced  into 
the  nickel,  the  mixture  will  have 
a  very  powerful  catalytic  action. 
Mixtures  of  6.7  per  cent  of  cobalt  or  copper  with  93.3  per  cent  of  nickel 
may  be  used;  they  are  obtained  by  the  reduction  of  the  mixed  ni- 
trates. The  process  is  not  confined  to  the  use  of  nickel;  it  is  stated 
that  other  metals  possessing  catalytic  action  can  be  used  with  equal 
effect. 

By  a  method  somewhat  similar  to  that  of  Bedford  and  Erdmann  the 
proposal  comes. from  Kast  J  to  prepare  catalysts  in  a  finely-divided  volu- 

*  Jour.  f.  prakt.  Chem.,  1913,  450. 

t  French  Patent  401,876,  April  8,  1909;  German  Patents  219,043  and  219,044, 
1908. 

t  U.  S.  Patent  1,070,138,  Aug.  12,  1912. 


THE  BASE  METALS  AS  CATALYZERS  129 

minous  condition  by  heating  the  trinitrophenol  salt  of  a  heavy  metal. 
These  salts  are  combustible  and  when  ignited  they  expand  greatly, 
so  the  resulting  ashes  (metal  or  metal  oxide)  are  found  to  be  in  a  volu- 
minous, spongy  form.  Kast  claims  that  the  usual  procedure  of  pre- 
cipitating a  salt  solution  (with  or  without  a  carrier)  yields  a  coarse 
crystalline  precipitate,  and  that  reduction  by  heating  in  a  reducing  gas 
slags  the  precipitate  in  consequence  of  which  the  catalytic  effectiveness 
is  considerably  diminished.  To  avoid  danger  of  an  explosion  when 
decomposing  the  trinitrophenol  compound  by  ignition  Kast  adds  oil 
or  tar  as  a  diluent.  He  also  recommends  for  this  purpose  nitrate  of 
ammonia,  as  this  salt  evolves  large  quantities  of  gas  on  heating  and 
leaves  no  residue.  The  formation  of  slag  which  Kast  objects  to  in 
ordinary  reduction  seemingly  would  be  aggravated  when  a  salt  of 
trinitrophenol  is  burned  under  these  conditions. 

The  hydrogenation  of  unsaturated  fatty  acids  and  their  esters 
may  be  effected,  according  to  deKadt,*  by  means  of  hydrogen  in  the 
presence  of  a  catalyst  consisting  of  a  soap  of  a  heavy  metal  or  of  a  noble 
metal,  made  from  a  fat  or  fatty  acid  having  a  melting  point  higher  than 
that  of  the  saturated  compound  to  be  produced.  For  example,  the 
nickel  soap,  or  preferably  a  mixture  of  the  nickel  and  iron  or  copper 
soaps  of  the  fatty  acids  of  stearine  or  Japan  wax,  is  dried  and  powdered, 
and  can  then  be  intimately  mixed  with  the  oil  to  be  hydrogenated. 
After  hydrogenation  the  oil  is  left  quiescent  at  a  temperature  above  its 
melting  point,  when  the  soap  particles  will  agglomerate  and  settle  on 
cooling.  If,  however,  the  oil  is  kept  in  motion  and  filtered,  the  soap 
does  not  pass  through  the  filter.  It  is  stated  that  this  process  is  more 
efficient  than  when  metallic  catalysts  are  used,  owing  to  the  more 
intimate  contact  between  the  catalyst  and  oil  or  fat  which  is  here 
obtained. 

Basic  compounds  of  high  molecular  fatty  acids  with  certain  of  the 
heavy  metals  are  proposed  as  catalyzer  formative  material  by  Hausa- 
mann.j  The  compounds  dissolve  in  the  oil  undergoing  treatment 
and  in  the  presence  of  hydrogen  afford  active  catalytic  bodies.  The 
temperatures  employed  range  from  100°  to  180°  C.  After  the  oil  has 
been  hardened  it  may  be  treated  with  dilute  acid  to  remove  the 
catalyzer.  J 

The  employment  of  a  basic  salt  of  a  heavy  metal  (nickel  or  copper) 
with  a  fatty  acid  is  recommended  by  De  Nordiske  Fabriker  De-No-Fa 
Aktieselskap  as  a  catalytic  material  in  the  hardening  of  fats  or  fatty 

*  British  Patent  18,310,  Aug.  9,  1912. 

t  Zeitsch.  f.  angew.  Chem.  (1914),  63,  No.  7. 

J  See  also  Seifen.  Ztg.  (1914),  7. 


130 


THE  HYDROGENATION  OF  OILS 


acids.  About  0.4  per  cent  of  the  metallic  compound  is  used  and  the 
hydrogenation  takes  place  at  temperatures  between  100°  C.  and 
180°  C.* 

Organic  compounds  of  metals,  such  as  metallic  salts  of  organic 
acids,  are  employed  by  Wimmer  and  Higgins  f  as  catalytic  agents  in 
the  reduction  or  hydrogenation  of  various  organic  compounds;  thus 
the  copper,  iron,  nickel  or  cobalt  salts  of  formic,  acetic  or  lactic  acid 

may  be  employed.  The  ad- 
vantage of  these  compounds  is 
that  they  can  readily  be  mixed 
with  the  compound  to  be  re- 
duced, either  in  the  form  of  a 
solution  or  as  an  "  emulsion  "; 
thus  the  compound  may  be 
emulsified  with  the  catalyst 
and  at  the  same  time  treated 
with  hydrogen.  It  is  stated 
that  hydrogenation  may  be  ac- 
celerated either  by  using  the 
hydrogen  under  pressure,  or 
by  impregnating  the  compound 

to  be  reduced  with  hydrogen, 
FIG.  44.  —  Photo-micrograph  of  nickel  pre-  -,  , ,  ,  .  .  •«.'••. 

cipitated  in  cottonseed  oil  by  the  action  of   and   then   ***««*   li   mt°   m~ 

hydrogen  on  nickel  resinate  dissolved  in   timate  contact  with  the  cata- 

the  oil.  X  100.  lyst.  One  detailed  example  is 

given  in  the  specification,  de- 
scribing the  treatment  of  100  grams  of  cottonseed  oil  with  hydrogen 
in  presence  of  1  to  5  grams  of  nickel  formate  at  a  temperature  of  170° 
to  200°  C. 

Wimmer  makes  the  statement  that  these  organic  salts  are  not 
reduced  to  the  metallic  condition  during  hydrogenation. { 

Bedford  and  Erdmann  §  state  that  nickel  formate  yields  nickel  sub- 
oxide  at  210°  C.,  while  metallic  nickel  is  formed  at  250°  C.,  and  that 
nickel  acetate,  oleate  and  linoleate  behave  in  a  similar  manner. 

Higgins  ||  uses  nickel  or  zinc  formate  in  the  reduction  of  organic 
compounds  without  the  application  of  gaseous  hydrogen. 

Several  other  methods  of  producing  catalyzers  have  been  the  sub- 

*  J.  S.  C.  I.,  1914,  324. 

f  French  Patent  441,097,  March  8,  1912. 

J  Seifen.  Ztg.  (1913),  1301. 

§  Zeitsch.  f.  ang.  Chem.  ref.  (1913),  751. 

II  Chem.  Ztg.  Rep.  (1913),  680;  British  Patent  23,377,  Oct.  12,  1912. 


THE  BASE  METALS  AS  CATALYZERS  131 

ject  of  the  patents  as,  for  example,  that  to  Crosfield  *  in  accordance 
with  which  kieselguhr  and  the  like  is  impregnated  with  a  solution 
of  nickel  sulfate  and  the  impregnated  material  treated  with  alkali 
hydrate  to  precipitate  nickel  hydrate  in  and  on  the  porous  material. 
The  product  is  then  well  washed,  dried  and  reduced.  If  kieselguhr 
is  used  the  powder  should  contain  about  30  per  cent  of  metallic  nickel. f 
A  similar  procedure  is  the  subject  of  a  patent  to  Kayser.  J  In  this 
case,  however,  the  nickel  sulfate  or  other  nickel  salt  in  concentrated 
solution  may  be  used  in  an  amount  to  saturate  kieselguhr  while  leaving 
it  in  an  apparently  dry  condition,  when  it  is  incorporated  with  a  molec- 
ular proportion  of  powdered  carbonate  of  soda  and  the  mixture  thrown 
into  boiling  water,  dried  and  reduced. 

Kayser  states  that  there  are  various  known  ways  for  producing  metallic  powders  in 
a  state  of  fine  division.  Nickel  powder,  which  for  many  purposes  is  recognized  as 
the  most  potent  catalyzer  technically  available,  is,  for  example,  most  conveniently 
produced  by  acting  upon  such  nickel  compounds  as  the  chloride,  oxide,  hydrate  or 
carbonate  at  an  adequate  temperature  with  hydrogen.  The  catalytic  energy  of 
such  a  powder,  however  carefully  prepared,  he  says,  is  at  best  an  uncertain  quantity; 
frequently  it  is  feeble,  as  sometimes,  for  no  conclusive  reason,  it  is  altogether  lack- 
ing. Furthermore,  powder  thus  produced  is  specifically  heavy  and  he  claims  can- 
not be  easily  kept  in  suspension  in  a  liquid  medium  like  oil,  when  that  is  desired, 
nor  can  it,  since  it  forms  an  almost  impervious  sediment,  be  readily  separated  and 
recovered  from  such  liquid  medium  by  a  contrivance  like  the  filter  press.  The  same 
objections,  he  says,  apply  to  nickel  powder  prepared  by  other  means;  and,  in  the. 
endeavor  to  improve  on  these,  Kayser  brings  a  compound  of  nickel,  such  as  the 
nitrate,  oxide,  hydrate  or  carbonate,  into  intimate  contact  with  an  inert,  absorptive 
and  comparatively  bulky  mineral  substance,  such  as  kieselguhr  and  infusorial  earth, 
dries  and  comminutes  the  product,  and  reduces  the  powder  thus  produced.  In  one 
case  he  saturates  kieselguhr  with  a  solution  of  nickel  nitrate,  dries  the  mixture, 
employing  in  the  case  of  the  nitrate  sufficient  heat  to  expel  the  nitric  acid,  grinds 
the  resulting  product  and  reduces  with  hydrogen.  Another  way  is  to  permeate 
or  saturate  kieselguhr  with  a  solution  of  nickel  chloride,  nickel  sulfate  or  other 
soluble  nickel  salt,  enter  the  resulting  product,  with  or  without  previous  drying,  into 
a  boiling  solution  of  carbonate  or  hydrate  of  soda  or  other  suitable  precipitant,  remove 
the  soluble  salts*  formed  by  washing,  dry  and  comminute  the  residue,  and  reduce 
it  as  before.  A  third  and  preferred  method,  as  stated,  is  to  saturate  the  kieselguhr 
with  a  solution  of  nickel  chloride,  nickel  sulfate  or  other  nickel  salt,  using  so  much 
solution  only  as  will  leave  the  kieselguhr  in  an  apparently  dry  and  freely  workable 

*  British  Patent  30,282,  1910. 

t  Ubbelodhe  and  Woronin  (Petroleum  (1911),  7,  9)  prepared  a  catalyzer  by  crush- 
ing a  plate  of  porous  clay  (which  had  been  ignited)  to  form  particles  of  about  the 
size  of  peas.  Nickel  nitrate  was  melted  and  heated  until  water  vapor  ceased  to  be 
evolved.  Then  the  clay  particles  were  added  and  the  mass  was  stirred  and  strongly 
heated  to  expel  the  oxides  of  nitrogen.  This  step  was  followed  by  reduction  with 
hydrogen  at  360°  C. 

t  U.  S.  Patent  1,004,034,  Sept.  26,  1911. 


132  THE  HYDROGENATION  OF  OILS 

condition,  incorporate  a  molecular  proportion  of  powdered  carbonate  of  soda  or 
other  powdered  precipitant,  throw  the  mixture  with  constant  stirring  into  boiling 
water,  remove  the  soluble  salts  formed  by  washing,  dry  and  comminute  the  mixture, 
and  reduce  as  before. 

To  develop  the  highest  catalytic  efficiency,  Kayser  states  that  the  kieselguhr  should 
become  evenly  and  completely  coated  and  permeated,  plated  as  it  were  with  a  film 
of  metal,  and  that  a  catalyzer  composed  of  one  to  two  parts  by  weight  of  metallic 
nickel  and  four  parts  by  weight  of  kieselguhr  has  however  proved  very  effective  in 
saturating  fats  and  oils  by  means  of  hydrogen.  The  author  can  see  no  advantage 
in  permeating  or  impregnating  the  interior  canals  of  the  carrier  with  catalytic  metal 
when  the  catalyst  is  to  be  used  for  hydrogenating  fatty  oils.  The  porous  support 
used  by  Sabatier  and  Senderens,  to  be  sure,  was  impregnated  with  reduced  nickel, 
but  these  investigators  directed  their  attention  to  the  hydrogenation  of  readily 
volatile  substances,  capable  of  diffusing  into  the  interior  of  the  nickel-laden  porous 
material. 

Seeking  to  overcome  the  disadvantage  of  ready  oxidation  in  the  air 
possessed  by  normal  catalytic  nickel,  Kayser  *  reduces  the  nickel 
oxide  or  equivalent  material  at  a  temperature  of  500°  to  600°  C.  and 
then  passes  through  the  reduced  material  a  brisk  current  of  carbonic 
acid  until  the  escaping  gas  proves  no  longer  inflammable.  By  this 
method  it  is  claimed  that  a  catalyzer  is  secured  which  will  remain  per- 
fectly cool  on  exposure  to  the  air  and  even  may  be  exposed  for  days 
without  losing  any  of  its  catalytic  energy,  a  result  which  probably  is 
due  to  elimination  of  occluded  hydrogen. f 

Wilbuschewitch  |  proposes  to  secure  more  rapid  u&skiction  of  cata- 
lyzer by  agitating  it  in  the  presence  of  hydrogen  in  a  heated  rotary 
drum.  The  temperature  during  the  treatment  is  stated  to  be  500°  C. 
Wilbuschewitch  §  has  patented  a  process  of  regenerating  spent  cata- 
lysts of  the  nickel  type,  involving  extraction  with  benzene,  treating 
with  alkali  solution,  acidifying,  treating  with  sodium  carbonate  solu- 
tion and  reducing. 

The  recovery  of  catalytic  material  is  described  by  Naamlooze 
Vennootschap,  Ant.  Jurgen's  Vereenigde  Fabrieken  in  British  Patent 
27,233,  1913.11  The  catalyzer  is  freed  from  organic  matter  by  heating 
in  a  current  of  air,  the  material  is  treated  with  an  acid  to  dissolve 
metal  from  its  insoluble  carrier  and  the  metal  is  then  precipitated  on 
the  same  carrier. 

*  U.  S.  Patent  1,001,279,  Aug.  22,  1911. 

t  The  Bremen-Besigheimer  Olfabriken  (Seifen.  Ztg.  (1913),  1007)  recommend 
the  exposure  of  catalytic  material  to  an  atmosphere  of  carbon  dioxide,  or  inert  gases. 
The  catalyzers  produced  in  this  manner  are  stated  to  be  permanent  and  to  possess 
great  activity. 

t  U.  S.  Patent  1,016,864,  Feb.  6,  1912. 

§  U.  S.  Patent  1,022,347,  April  2,  1912. 

II  Seifen.  Ztg.  (1914),  169. 


THE  BASE  METALS  AS  CATALYZERS 


133 


Bedford  and  Erdmann  *  treated  a  quantity  of  used  nickel  oxide  cata- 
lyzer with  dilute  sulfuric  acid.  Hydrogen,  accompanied  by  hydro- 
carbons of  disagreeable  odor,  was  evolved.  A  carbonaceous  residue 
amounting  to  6  or  7  per  cent  remained  after  treatment  with  the  acid. 
Nickel  oxide  has  been  found  to  take  up  silica  when  used  repeatedly  as  a 
catalyzer.  The  same  absorption  of  silica  also  occurs  with  palladium. 


FIG.  45. 


Wilbuschewitsch,  in  U.  S.  Patent  1,029,901,  of  June  18,  1912,  de- 
scribes a  process  of  making  a  catalyst  in  which  he  takes,  for  example, 
nickel  sulfate  in  the  form  of  a  solution  of  strength  of  10  to  14  degrees 
Baume,  mixing  this  with  about  double  its  weight  of  an  inorganic 
substance  such  as  clay,  asbestos,  pumice  stone,  kieselguhr  or  the  like, 
from  which  all  soluble  matter  has  been  removed  by  treatment  with  an 
acid.  The  mixture  is  then  treated  with  carbonate  of  soda  to  convert 
the  metal  salt  into  a  carbonate.  The  composition  is  heated  to  about 
500°  C.  so  as  to  transform  the  carbonate  into  the  oxide.  Reduction 
with  hydrogen  is  then  carried  out  and  the  product  is  ground  with  oil 
until,  as  the  patentee  states,  a  strongly  viscous  liquid,  similar  in 
character  to  an  emulsion,  is  produced. 

An  apparatus  employed  by  Wilbuschewitsch,  f  Fig.  45,  for  the  re- 

*  Jour.  f.  prakt.  Chem.,  1913,  444. 

t  U.  S.  Patent  1,029,901,  June  18,  1912. 


134  THE  HYDROGENATION  OP  OILS 

» 

duction  of  nickel  compounds  consists  of  a  cylindrical  drum  6  mounted 
to  rotate  on  rollers  m  and  provided  with  a  heating  jacket  o.  The 
material  is  charged  into  the  drum  through  an  inlet  opening  n.  To  one 
of  the  end  plates  of  the  drum  a  tubular  shaft  c  is  secured  which,  with 
its  free  end,  is  guided  in  a  stuffing  box  k  supported  in  a  lateral  stud  of  a 
tubular  receptacle  d.  On  the  shaft  a  spur  gear  q  is  mounted  which  is 
in  mesh  with  a  pinion  gi  adapted  to  be  rotated  by  means  of  a  belt 
pulley  r.  By  means  of  the  gearing  q',  q  the  drum  6  is  slowly  rotated, 
and  during  such  rotation  it  is  heated  to  about  500°  C.  Hydrogen  is 
then  forced  into  the  drum  through  a  pipe  a  located  coaxially  within 
the  hollow  shaft  c  and  connected  at  one  end  to  a  tube  i.  The  hydrogen 
is  passed  through  the  material  to  be  reduced,  and  from  the  latter  it 
is  successively  conducted  through  an  automatically  operating  dust 
collector  9  connected  to  the  retort,  a  cooling  worm  /  and  purifying 
vessels  g,  gf  containing  respectively  acid  and  caustic  soda  lye,  or  a 
similar  purifying  medium.  After  thus  being  regenerated  it  is  returned 
by  means  of  a  pump  h.  The  water  produced  by  the  reduction  is  con- 
densed in  the  coil  /  and  is  dropped  from  the  coil  /  into  the  vessel  d 
from  which  it  is  withdrawn  through  an  overflow  e.  The  dust  collector 
9  by  means  of  which  the  hydrogen  escaping  from  the  drum  is  pre- 
vented from  carrying  along  particles  of  dust  is  constructed  in  the  form 
of  a  worm  conveyor  /.  The  dust  moves  through  the  hollow  shaft  c  in 
the  direction  of  the  gas  flow  and  owing  to  the  difference  in  the  speed 
of  the  gas  and  dust  the  latter  is  deposited  on  the  bottom  of  the  shaft  c, 
and  is  conveyed  back  into  the  retort  by  the  worm  I. 

A  procedure  noted  in  connection  with  Crosfields  &  Sons,  Ltd.,  vs. 
Techno-Chemical  Laboratories,  Ltd.,*  disclosed  as  apparatus  a  cylin- 
drical autoclave  1  meter  high  and  f  meter  in  diameter  (inside  measure- 
ments), with  a  steam  jacket,  and  fitted  with  a  non-conducting  lining 
of  unknown  material.  Nine  kilograms  of  cotton  oil  were  pumped 
into  the  autoclave,  and  288  grams  of  a  composition,  containing  a 
catalytic  agent,  were  used  and  were  mixed  with  the  oil  prior  to 
the  introduction  of  the  mixture  into  the  autoclave.  The  autoclave 
was  then  filled  with  hydrogen  from  a  cylinder  to  a  pressure  of  15 
atmospheres.  During  the  operation  the  pressure  varied  from  time 
to  time  according  to  the  absorption  of  hydrogen.  A  mechanically 
driven  circulation  pump  was  connected  with  the  autoclave  both  by 
its  suction  and  delivery  conduits.  By  means  of  a  pump  and  a  jet 
for  spraying,  a  mixture  of  oil  and  composition  containing  the  catalytic 
agent  was  drawn  from,  and  forced  back  into,  the  autoclave.  The 
iodine  absorption  was  not  determined.  The  composition  containing 

*  British  Official  Journal  Supplement,  June  18,  1913,  301. 


THE  BASE  METALS  AS  CATALYZERS  135 

the  catalytic  agent  was  prepared  from  a  salt  of  nickel.  The  catalyst 
employed  was  prepared  as  follows:  About  1^  kilograms  of  nickel 
sulfate  were  dissolved  in  3  liters  of  water,  and  the  same  weight  of 
sodium  carbonate,  dissolved  in  the  same  quantity  of  water,  and  at 
about  70°  to  80°  C.  was  added  to  the  nickel  sulfate,  which  was  at 
60°  to  70°  C.  The  mixture  was  stirred  for  1|  to  2  hours,  and  the  pre- 
cipitate was  filtered  off  and  washed  with  distilled  water  at  about  25°  C. 
for  60  to  70  hours  alternately  in  tanks  and  filter  press.  A  small  sample 
was  dried  and  tested  to  ascertain  that  the  precipitate  had  been  suffi- 
ciently washed.  The  washed  precipitate  was  dried  in  hot  air  at  80° 
to  85°  C.,  and  was  calculated  to  weigh  720  grams.  It  was  then  roasted 
in  a  pan  for  about  15  minutes  over  an  open  Bunsen  gas  burner,  and 
the  weight  after  roasting  was  calculated  to  be  about  380  grams.  The 
product  was  heated  to  about  300°  C.  for  about  6  minutes  in  a  current 
of  hydrogen  in  revolving  glass  tubes  slightly  inclined,  the  precipitate 
being  introduced  at  the  higher  end  and  through  a  spiral  glass  tube, 
and  the  hydrogen  at  the  lower  end.  The  product,  which  weighed  288 
grams,  was  directly  introduced  into  a  small  quantity  of  oil,  which  was 
mixed  with  the  9  kilos  the  following  day. 

Catalyzers  said  to  possess  high  activity  are  produced  by  mixing 
with  oil  a  base-metal  compound  of  an  easily-reducible  character  and 
yielding  the  catalytic  metal  on  reduction,  heating  and  bringing  a 
reducing  gas  under  pressure  into  contact  with  this  mixture.* 

Nickel  carbonyl  is  employed  by  Franck  f  to  form  catalytic  material 
by  precipitation  of  nickel  from  the  carbonyl  in  an  oil  menstruum  in  the 
presence  of  solid  material.  The  latter  may  be  kieselguhr  or  nickel 
or  copper  oxides  or  reducible  metallic  salts.  The  solid  material  is 
heated  with  the  oil  and  nickel  carbonyl  conducted  into  the  mixture. 

Eldred  J  does  not  regard  a  finely-divided  catalyst  as  desirable  as 
one  having  a  catalytic  metal  welded  to  a  heat-conducting  support. 
He  states  that  since  the  amount  of  such  catalytic  action  performed 
in  a  given  time  unit  in  a  body  of  gas  is  strictly  proportionate  to  the 
exposed  surface  of  catalyzing  metal,  it  is  customary  to  use  such  metals 
in  finely-divided  form,  sometimes  as  masses  of  powder  and  sometimes 
as  powders  adhering  to  and  held  by  inert  porous  materials,  such 
as  asbestos,  glass  wool  and  the  like,  but  that  these  expedients  while 
giving  great  surface  to  a  given  amount  of  metal  do  not  give  a  pro- 
portionately great  exposure  of  such  metal  to  the  gases  or  vapors  to 
be  treated.  It  is  substantially  impossible  to  drive  or  distribute  gases 

*  Seifen.  Ztg.,  1913,  1298. 
t  Seifen.  Ztg.,  1913,  1271. 
\  U.  S.  Patent  1,043,580,  Nov.  5,  1912. 


136  THE  HYDROGENATION  OF  OILS 

uniformly  throughout  a  body  of  powder,  and  in  passing  gases  over  a 
body  of  such  powder  it  is  substantially  only  the  top  layers  of  the 
powder  which  display  a  maximum  activity,  underlaying  layers  not 
functioning  to  any  great  extent.  Use  of  very  thin  layers  of  powder 
of  course  necessitates  unduly  extended  shelf  surface.  Eldred  observes 
that  nearly  all  catalyses  are  exothermic  reactions,  heat  being  developed 
.by  the  action,  and  frequently  the  amount  of  heat  is  rather  large.  And 
as  it  is  usually  desirable  to  work  within  comparatively  narrow  tem- 
perature limits,  keeping  and  maintaining  the  catalytic  metal  within  a 
few  degrees  of  some  definite  temperature,  this  evolution  of  heat  may 
become  a  serious  matter.  Nearly  all  the  catalytically  acting  metals 
in  the  form  of  powders  are  relatively  poor  conductors  of  heat.  When, 
for  example,  platinum  is  distributed  through  a  mass  of  such  a  heat 
insulator  as  asbestos,  it  is  very  hard  to  prevent  the  accumulation  of 
reaction  heat  in  the  metal.  Hence  Eldred  proposes  a  catalytic  body 
comprising  the  catalytic  metal  in  the  form  of  a  very  thin  continuous 
layer  or  film  supported  by  masses  of  better  heat-conducting  metals 
weld-united  to  such  layer  or  film  and  therefore  in  absolute  metallic 
union  therewith  so  that  by  controlling  the  temperature  of  the  carrying 
metal  the  temperature  of  the  film  or  layer  can  also  be  controlled.  A 
catalyst  may  be  made  by  welding  a  sheath  or  coating  of  platinum  on  a 
billet  of  copper  or  steel  and  "  coextending  "  the  joined  metals  to  form 
wire  or  sheet  metal.  If  3  to  10  per  cent  of  platinum  be  placed  on  the 
original  billet  and  coextension  be  performed  with  care,  the  wire,  sheet 
or  leaf  metal  formed  will  also  have  3  to  10  per  cent  of  platinum,  but 
this  thickness  in  such  coextended  ware  will  correspond  to  an  extremely 
tenuous  layer.  Cobalt  and  nickel  may  be  united  to  steel  or  copper 
billets,  and  the  duplex  or  compound  billets  extended  in  similar  manner 
to  produce  catalysts  having  film  coatings  of  cobalt  or  nickel.  The 
cobalt  or  nickel  may  be  united  to  the  underlying  core  metal  directly 
or  through  a  linking  layer  of  another  metal  such  as  gold,  silver  or 
copper.  Eldred  mentions  the  cobalt  and  nickel  catalyzers  as  useful 
in  hydrogenation  reactions. 

In  the  preparation  of  a  catalytic  body  Ellis  *  recommends  the  use 
of  wood  charcoal  which  possesses  the  property  of  absorbing  or  occlud- 
ing hydrogen  and  when  incorporated  with  nickel  or  other  metal  catalyst 
serves  as  an  activator  and  storehouse  of  hydrogen.  If  nickel  is  used, 
a  ratio  of  one  part  of  metal  to  four  parts  of  charcoal  is  best  not  ex- 
ceeded. The  metallic  compound  may  be  precipitated  more  or  less 
on  the  surface  of  the  charcoal  particles  by  wetting  the  latter  with  a 
solution  of  a  precipitant  and  adding  a  solution  of  a  nickel  salt.  Pre- 
*  U.  S.  Patent  1,060,673,  of  May  6,  1913. 


THE  BASE  METALS  AS  CATALYZERS  137 

cipitation  under  these  conditions  is  largely  external.  Exposure  of 
the  composition  to  the  air  after  reduction  is  to  be  avoided.* 

Miiller  f  finds  the  catalytic  activity  of  iron  and  nickel,  especially  in 
connection  with  processes  for  the  introduction  of  hydrogen  into  gly- 
cerides  of  unsaturated  fatty  acids,  is  considerably  augmented  and 
caused  to  resemble  in  activity  the  catalytic  properties  of  the  noble 
metals,  such  as  palladium,  if  the  former  metals  after  ignition  in  hydro- 
gen are  heated  in  a  stream  of  carbonic  acid  gas  in  order,  apparently, 
to  destroy  the  metal  hydrides  which  are  formed  and  convert  the  cata- 
lyzer into  the  pure  metal.  Miiller  says  the  process  also  makes  pos- 
sible the  elimination  of  finely-divided  catalyzer,  whose  production  and 
application  the  patentee  states  is  accompanied  with  many  difficulties, 
and  its  replacement  by  coarse  fragments  of  metal,  such  as  filings  and 
shavings  of  iron,  nickel  and  copper,  first  igniting  the  latter  in  hydrogen 
and  then  in  carbonic  acid  gas.  He  states  that  common  iron  filings 
caused  a  reduction  of  the  iodine  number  of  only  2|  per  cent  in  two 
hours,  while  using  filings  which  had  been  treated  with  carbon  dioxide 
the  iodine  number  was  reduced  25  per  cent. 

When  nickel  hypophosphite  solution  is  boiled,  metallic  nickel  is 
precipitated,  under  some  conditions  as  thin  metallic  leaves;  under 
other  conditions  as  a  fine  powder.  The  latter  form  acts  catalytically 
on  sodium  hypophosphite  in  solution  giving  acid  sodium  phosphite 
with  evolution  of  hydrogen.  The  powder  form  is  obtained  by  dis- 
solving 20  grams  nickel  sulfate  in  100  cc.  water,  heating  on  a  water 
bath,  introducing  in  one  addition  70  grams  sodium  hypophosphite 
and  stirring.  At  the  end  of  one  hour  reduction  is  complete.  Dis- 
tilled water  is  added,  the  nickel  material  is  allowed  to  settle  and  is 
washed  by  decantation.J  Palladium  prepared  in  a  somewhat  similar 
manner  decomposes  sodium  hypophosphite  very  effectively.! 

On  account  of  the  relatively  low  degree  of  sensitiveness  of  nickel 
oxide  catalyzers  to  the  usual  catalyzer  poisons  Erdmann  ||  was  able  to 
readily  hydrogenate  Japanese  fish  oil  containing  a  high  content  of  free 
fatty  acid  and  also  certain  sulfur-containing  oils,  such  as  Egyptian 
cottonseed  oil. 

If  the  hardening  operation  is  interrupted  before  the  reaction  is  com- 

*  See  also  Ellis,  U.  S.  Patent  1,088,673,  Feb.  24,  1914. 

t  Seifen.  Ztg.  (1913),  747;  French  Patent  540,703  (1912);  British  Patent  22,092, 
Sept.  28,  1912,  to  Miiller  Speisefettfabrik. 

i  The  author  has  noted  that  this  precipitated  nickel  material  is  catalytic  and 
readily  acts  to  harden  cottonseed  oil  at  a  temperature  of  210°  C.,  or  thereabouts, 
with  hydrogen  at  atmospheric  pressure. 

§  Breteau,  Bull.  Soc.  Chim.  (1911),  9,  515-519. 

II  Chem.  Ztg.,  1913,  1142,  1173  and  1195. 


138  THE  HYDROGENATION  OF  OILS 

plete,  and  the  catalyzer  collected  by  centrifuging,  extraction  with 
benzol  or  other  solvents  shows  the  rate  of  removal  of  the  residual  fatty 
substances  from  the  catalyzer  to  be  very  slow.  The  fat  clings  strongly 
to  the  catalytic  body.  On  the  contrary  when  the  reaction  is  at  an  end 
the  catalyzer  separates  in  a  flocculent  condition.  Because  of  this, 
Erdmann  is  of  the  opinion  that  the  oxide  and  unsaturated  fat  form 
a  loose  addition  compound  which  is  subsequently  split  by  hydrogen. 
Analysis  of  the  black  nickel  material  obtained  by  extracting  the  fat 
from  used  catalyzer  shows  several  per  cent  of  carbon  to  be  present, 
apparently  united  to  the  nickel  as  a  kind  of  carbide.  The  greater 
portion  of  the  used  catalyzer  consists  of  a  mixture  of  nickel  oxide  and 
suboxide.  The  latter  is  looked  upon  as  Ni2O,  described  by  Bellucci 
and  Corelli.*  The  hydrogen  transference  probably  takes  place  in 
one  of  two  ways:  either  an  intermediate  phase  represented  by  the 
compounds 


x  H. 

>0    and  \0 

HC    -Ni/  . 


is  formed  (the  latter  compound  carrying  its  hydrogen  very  loosely 
bound)  ;  or  a  decomposition  of  water  may  take  place  in  accordance 
with  the  reaction 

Ni2O  +  H20  =  2NiO  +  H2 

yielding  hydrogen  in  a  nascent  state  which  is  assumed  to  unite  with 
the  unsaturated  fat,  while  the  nickel  oxide  formed  is  reduced  to  the 
suboxide  by  hydrogen  in  the  molecular  condition.  Which  of  these 
views  is  correct  can  be  ascertained  only  by  further  investigations. 
Hydrated  nickel  oxide  or  nickel  carbonate  may  be  used  in  place  of  the 
oxide,  and  under  some  conditions  apparently  also  nickel  salts  such  as 
the  formate  and  acetate.  These  salts  act  as  hydrogen  carriers  only 
after  the  acid  radical  has  been  split  up  and  the  free  metallic  oxide 
formed. 

The  conclusion  is  reached  by  Bedford  and  Erdmann  f  that  some  of 
the  organic  salts  of  nickel  act  like  nickel  oxide  as  catalyzers  and  form 
in  fact  nickel  oxide  by  decomposition  when  heated  in  the  presence  of 
hydrogen.  A  number  of  tests  were  carried  out  using  nickel  formate, 
acetate,  oleate  and  linoleate.  In  one  case  200  grams  of  cottonseed  oil 
were  heated  to  253°  C.  with  nickel  formate  (equivalent  to  2.4  grams 

*  Atti.  R.  Accad.  dei  Lincei,  22,  I,  603  and  703. 
t  Jour.  f.  prakt.  Chemie,  1913,  449. 


THE  BASE  METALS  AS  CATALYZERS 

NiO),  and  hydrogen  passed  into  the  mixture.  The  oil  quickly  darkened 
due  to  the  formation  of  finely-divided  nickel  and  nickel  oxide.  After 
one  and  one-half  hours  the  solidifying  point  of  the  fatty  product  was 
51.2°  C.  200  grams  of  cottonseed  oil,  6  grams  of  nickel  acetate  and 
20  cc.  of  water  were  heated  and  hydrogen  passed  therethrough.  The 
temperature  was  brought  to  215  to  220  degrees.  The  acetate  retained  its 
green  color  unchanged  and  no  hardening  of  the  oil  was  observed.  The 
temperature  was  then  raised  to  240  to  250  degrees  when  the  mixture 
turned  black  and  in  one  and  one-half  hours  the  solidifying  point  of  the 
hardened  oil  was  49  degrees.  250  cc.  linseed  oil  with  6.3  grams  of 
nickel  linoleate  (equivalent  to  1.2  gram  NiO)  was  treated  with  hydro- 
gen at  2.65  degrees  for  three  hours  yielding  a  product  having  a  solidi- 
fying point  of  44.5°  C.  The  catalyzer  at  the  close  of  the  test  consisted 
of  nickel  oxide  and  suboxide  and  nickel  soap.  Using  11.5  grams  of 
nickel  oleate  to  200  grams  of  cottonseed  oil  it  was  found  that  the  black 
coloration  occurred  above  220  degrees.  Hydrogenation  was  carried  on 
at  250  degrees  and  after  two  hours  the  solidifying  point  was  41  degrees. 
On  the  glass  walls  of  the  reaction  flask  a  brilliant  mirror  of  metallic 
nickel  formed,  which  in  the  course  of  time  separated  in  coarse  flakes. 

A  catalyzer  which  remains  easily  in  suspension  is  prepared  accord- 
ing to  the  Bremen-Besigheimer  Olfabriken  *  by  incorporating  a 
metal  salt  with  an  inorganic  carrier  and  drying  this  product  in  the 
presence  of  the  unsaturated  material  which  is  subsequently  to  be 
hydrogenated,  or  for  that  matter  with  any  suitable  indifferent  liquid. 
The  mixture  is  treated  so  as  to  expel  all  of  the  water  and  a  part  of  the 
volatile  acid  of  the  salt  which  otherwise  might  become  free  and  act 
injuriously  during  the  reduction  process. 

By  this  removal  of  water  and  acid  the  catalyzer  is  put  into  such  a 
condition  that  it  is  capable  of  remaining  suspended  in  oils  and  fats. 
In  the  application  of  the  catalyzer  for  the  reduction  of  the  latter  a 
carrier,  such  as  kieselguhr,  asbestos  and  the  like,  is  treated  with  a 
solution  of  a  metallic  salt,  such,  for  example,  as  nickel  acetate.  After 
drying  the  material  it  is  ground  with  a  quantity  of  oil  so  as  to  yield 
the  catalyzer  in  an  extremely  finely-divided  condition  and  disseminated 
through  the  oil  vehicle.  The  water  and  acetic  acid  are  now  removed 
by  heating  the  mixture  to  150°  to  200°  C.  in  a  closed  vessel  fitted  with 
an  agitator  and  vacuum  pump.  After  the  volatile  material  has  been 
removed  by  such  a  treatment,  hydrogen  is  conducted  through  the 
resulting  product. f 

*  Zeitsch.  f.  angew.  Chem.  (1913),  Ref.  604. 

t  A  form  of  treatment  of  oil  and  catalyzer  with  hydrogen,  as  disclosed  by  the 
Besigheimer  Olfabriken,  is  noted  in  Seifen.  Ztg.  (1913),  1007. 


140  THE  HYDROGENATION  OF  OILS 

Higgins  *  states  that  the  conversion  of  unsaturated  fatty  acids  or 
their  glycerides  or  other  unsaturated  compounds  into  the  correspond- 
ing saturated  compounds,  by  means  of  hydrogen  in  presence  of  finely- 
divided  nickel  or  other  metal,  is  accelerated  by  the  presence  of  formic 
acid  or  other  volatile  organic  acid.  From  1  to  2  per  cent  of  formic 
acid,  calculated  on  the  weight  of  unsaturated  material,  has  been  found 
a  suitable  proportion.  The  hydrogen  may  be  passed  through  a  vessel 
containing  the  volatile  acid  before  admitting  it  to  the  mixture  of 
unsaturated  compound  and  metal. 

According  to  Wimmer  and  Higgins  f  catalytic  material  may  be 
prepared  from  nickel  salts,  such  as  nickel  formate,  by  mixing  with  a 
protecting  material,  the  latter,  for  example,  being  an  oily  body,  and 
then  reducing  the  salt  to  yield  the  nickel  in  a  metallic  condition.  The 
oil  serves  to  preserve  the  catalytic  properties  of  the  reduced  substance. 

Wimmer  has  observed  that  the  content  of  free  fatty  acid  is  increased 
by  hydrogenation  and  has  offered  as  a  remedy  the  addition  of  drying 
agents  to  the  catalytic  material.  Ignited  sodium  or  magnesium  sulfate 
are  recommended  for  the  purpose.  In  hardening  cottonseed  oil  Wim- 
mer uses  3  to  10  per  cent  of  sodium  sulfate  and  2  to  3  per  cent  of  nickel 
formate  calculated  on  the  weight  of  the  oil.  He  found  a  sample  of 
peanut  oil  'containing  0.5  per  cent  of  fatty  acid,  after  hardening  in  this 
manner,  to  contain  0.42  per  cent  of  fatty  acid,  while  without  an  addition 
of  sodium  sulfate  the  acid  content  was  0.72  per  cent.| 

A  flaky  form  of  nickel  catalyzer  is  brought  forward  by  Hagemann 
and  Baskerville  §  to  replace  nickel  supported  on  an  inert  carrier. 
They  observe  that  the  application  of  the  latter  type  of  catalyzers 
involves  a  number  of  technical  difficulties;  for  instance,  on  account 
of  their  finely-divided  state,  such  catalyzers  cannot  be  readily  and 
satisfactorily  separated  and  recovered  from  the  fats,  and,  owing  to 
their  density,  do  not  remain  well  suspended  in  the  oil  treated,  when 
such  suspension  is  desired.  The  use  of  a  metal  precipitated  upon  an 
inert  carrier,  such  as  kieselguhr,  they  note,  has  not  given  entirely 

*  British  Patent  18,282,  Aug.  8,  1912. 

t  French  Patent  454,501,  Feb.  18,  1913.  When  nickel  formate  is  used,  it  serves 
both  as  reducing  agent  and  as  catalyst;  with  zinc  formate,  addition  of  a  known 
catalyst,  such  as  palladium  chloride,  is  desirable.  The  temperature  used  is  pref- 
erably about  20°  C.  below  that  at  which  the  formate  would  decompose  into  the 
oxalate  at  the  pressure  existing  during  the  operation.  (Higgins,  British  Patent 
23,377,  Oct.  12,  1912.)  Wimmer  and  Higgins  (Seifen.  Ztg.,  1914,  7)  state  that  the 
metal  salts  of  organic  acids  may  be  used  for  the  hydrogenation  of  various  organic 
compounds  of  an  unsaturated  nature  in  addition  to  oils  and  fats. 

t  Seifen.  2tg.,  1<U4,  390. 

§  U.  S.  Patent  1,083,930,  Jan.  13,  1914. 


THE  BASE  METALS  AS  CATALYZERS  141 

satisfactory  results,  probably  for  the  reason  that  only  a  small  part 
(one  side)  of  the  film  of  the  precipitated  metal  comes  into  actual  con- 
tact with  the  liquid  to  be  reduced  and  the  hydrogen,  and  the  remainder 
of  the  metal  is  consequently  inactive,  since  the  reacting  materials 
cannot  come  into  contact  therewith.  Other  stated  objections  to  the 
use  of  such  a  catalyst  are  that  the  process  of  revivification  is  quite  an 
expensive  undertaking,  since  the  metal  must  be  dissolved  in  an  acid, 
and  reprecipitated  upon  kieselguhr;  that  it  is  difficult  to  obtain  a 
catalyzer  by  precipitation  and  reduction  methods,  which  is  free  from 
oxides  and  other  impurities;  and  that  fatty  oils  hydrogenated  with 
such  finely-divided  catalyzers  will  contain  metallic  soaps,  such  as 
soaps  having  a  nickel  base,  which  are  undesirable  from  economic 
and  hygienic  standpoints.  Hagemann  and  Baskerville  observe  that 
metals  having  catalytic  activity,  such  as  nickel,  or  cobalt,  brought  into 
a  state  of  extremely  thin  films,  or  flakes,  by  mechanical,  chemical  or 
galvanoplastic  processes,  as,  for  example,  by  the  method  shown  by 
Edison,*  offer  technical  advantages  as  catalysts  in  the  hydrogenation 
of  fatty  oils.  These  films,  or  flakes,  are  obtainable  in  a  state  of  high 
purity,  and  may  be  employed  either  in  the  metallic  (pure)  state  or 
after  being  partially  oxidized.  Films  can  readily  be  prepared,  having 
a  thickness  of  from  one  twenty-thousandth  to  one  forty-thousandth 
of  an  inch,  and  accordingly  the  efficiency  of  a  given  weight  of  a  cata- 
lytic metal,  for  example,  nickel,  when  applied  in  this  form,  is  high, 
owing  to  the  large  amount  of  exposed  surface.  Such  films,  or  flakes, 
will,  on  account  of  their  extreme  thinness,  readily  float  and  remain 
evenly  distributed  throughout  the  whole  mass  of  fats  or  oils.f  The 
separation  of  the  hardened  products  from  the  flaky  nickel,  cobalt,  etc., 
is  said  to  be  accomplished  without  difficulty.  In  the  revivification 
and  recovery  of  the  catalyzer  for  subsequent  use  it  has  been  found 
that  flaky  metals,  as  nickel,  etc.,  admit  of  economical  treatment,  for 
the  flakes  retain  their  physical  form.  In  this  revivification  the  flakes, 
or  films,  from  which  the  fat  has  been  removed  (for  example,  by  ex- 
traction with  a  suitable  solvent)  are  subjected  to  superficial  oxidation 
followed  by  reduction  with  hydrogen  at,  say,  300°  C.,  or  higher,  in  a 
current  of  oxygen  or  air,  or  by  treatment  with  oxidizing  agents  in 
liquids  in  which  the  metallic  flakes  are  suspended.  In  such  a  manner 
Hagemann  and  Baskerville  state  they  can  repeatedly  produce  freshly- 
reduced  surfaces  to  both  sides  of  the  metal  flakes,  or  films,  without 

*  U.  S.  Patent  865,688.    See  also  821,626. 

t  The  author  has  made  use  of  a  form  of  flaky  nickel  derived  from  nickel  carbonyl 
in  hydrogenating  oils  and  has  found  this  form  of  the  metal  to  be  satisfactory  from 
the  catalytic  standpoint. 


142  THE  HYDROGENATION  OF  OILS 

having  recourse  to  conversion  of  the  metal  into  a  soluble  salt,  precipi- 
tating, igniting  and  reducing. 

Another  method*  of  forming  a  catalyzer  involves  the  utilization  of 
the  disintegrating  effect  of  an  electrical  current  or  arc  between  a  pole  or 
poles  of  nickel  immersed  in  a  vehicle  offering  considerable  resistance  to 
the  electric  current,  such  as  water,  or  aqueous  solutions,  thereby  pro- 
ducing nickel  material  in  a  finely-divided  condition,  requiring  little  or 
no  further  treatment  to  serve  as  a  catalyzer.  For  example,  two  elec- 
trodes of  pure  nickel  in  bar  or  rod  form  are  connected  one  to  the  positive 
and  the  other  to  the  negative  pole  of  a  source  of  electricity.  The  ends 
of  the  nickel  rods  are  dipped  in  water  and  brought  in  contact,  then  sep- 
arated so  as  to  form  an  arc  under  the  water.  This  results  in  the  pro- 
duction of  nickel  material  usually  of  a  brown  to  blackish  color  in  a  state 
of  more  or  less  fine  division,  some  of  this  material  often  being  so  fine 
and  flocculent  as  to  remain  suspended  in  water  for  several  days.  Dis- 
tilled water  should  preferably  be  used  though  under  some  circumstances 
saline  solutions  may  be  employed.  By  the  use  of  distilled  water  the  in- 
troduction of  contaminating  bodies  is  practically  or  entirely  avoided. 

Careful  regulation  of  the  arc  is  desirable  in  order  to  avoid  melting 
away  particles  of  nickel  in  the  shape  of  large  fragments  which  are  not 
useful  for  the  present  purpose,  although  some  coarse  material  is  usually 
formed.  When  the  product  contains  such  heavy  nickel  particles  it 
may  be  levigated  and  the  lighter  sludge  separated  from  the  heavy 
nickel  residue.  The  sludge  is  evaporated  to  dryness  when  a  very  light 
nickel  material  is  obtained,  which  may  be  used  at  once  as  a  catalytic 
body  or  may  first  be  reduced  in  hydrogen.  Or,  the  wet  sludge  may  be 
heated  with  oil  to  expel  the  water  in  order  to  produce  a  form  of  nickel 
which  remains  suspended  in  oil  for  a  long  period  and  this  may  be  used 
as  catalytic  basis.  In  such  a  case  it  is  usually  well  to  heat  to  230  to 
250°  C.  in  the  early  stage  of  the  hydrogenation  treatment  and  after  a 
time  the  temperature  may  be  reduced  to  200  degrees  and  lower. 

Boberg  f  prepares  a  catalyst  by  reduction  with  hydrogen  of  a  metal- 
lic compound,'  such  as  ignited  nickel  carbonate,  under  such  conditions 
that  the  resulting  product  is  a  complex  compound  of  one  or  more  sub- 
oxides  of  the  metal.  The  preferred  range  of  temperature  during  re- 
duction is  from  230°  to  270°  C.,  the  material  being  heated  for  a  longer 
period  the  lower  the  temperature  employed.  It  is  stated  that  unneces- 
sarily protracted  heating  should  be  avoided  as  leading  to  a  more  com- 
plete reduction  with  loss  of  activity  in  the  product. 

The  product  may  be  collected  for  immediate  use  in  the  medium  in 

*  Ellis,  U.  S.  Patent  1,092,206,  April  7,  1914. 
f  U.  S.  Patent  1,093,377,  April  14,  1914. 


THE  BASE  METALS  AS  CATALYZERS  143 

which  it  is  to  be  used,  e.g.,  oil,  but  if  not  required  at  once  slow  oxidation 
in  the  atmosphere  can  be  allowed,  provided  local  overheating  is  pre- 
vented (which  leads  to  excessive  oxidation)  and  the  material  can  then 
be  kept  without  special  precautions  against  oxidation  and  restored  to 
full  activity  when  required.  For  instance  the  material  may  be  col- 
lected in  water  and  then  filtered  therefrom  and  allowed  to  dry  in  the  air 
or  may  be  collected  in  an  atmosphere  of  hydrogen,  which  is  then  slowly 
replaced  by  oxygen  or  air. 

In  order  to  prepare  it  for  use  the  material  only  requires  to  be  heated 
for  say  one  to  two  hours  at  about  180°  C.  in  an  atmosphere  of  hydrogen 
or  the  catalyst  may  be  treated  with  hydrogen  when  in  suspension  in  a 
suitable  liquid.  When  the  catalyst  is  used  for  hardening  fats  or  oils  no 
special  treatment  of  this  kind  is  necessary  as  the  catalyst  acquires  its 
full  activity  in  the  early  stages  of  the  process. 

The  catalyst  may  be  prepared  by  reducing  to  nickel  as  completely 
as  possible  one  of  the  oxides  of  nickel  and  oxidizing  this  product  with 
air  or  oxygen  diluted  with  an  inert  gas,  the  proportion  of  oxygen  being 
regulated  to  avoid  local  overheating.  This  oxidizing  action  can  be 
carried  out  at  between  300°  and  600°  C. 

Boberg  states  that  he  has  "made  experiments  with  various  prod- 
ucts of  reduction  and  has  obtained  the  following  results:  The  prod- 
uct of  reduction  of  such  a  composition  that  an  ultimate  analysis  gives 
a  proportion  of  nickel  to  oxygen  corresponding  to  an  imaginary  formula 
Ni9.30,  i.e.,  but  little  suboxide,  produced,  in  a  certain  time,  hardening 
of  a  liquid  fat  up  to  a  melting  point  of  40°  C.,  whereas,  a  product  corre- 
sponding to  an  imaginary  formula  Ni2.650  gave  in  the  same  time  and 
for  the  same  material  hardening  corresponding  to  a  melting  point  of 
58°  C.  It  appeared,  however,  that  with  a  lesser  proportion  of  nickel  in 
the  product,  i.e.,  a  composition  that  apparently  indicated  the  presence 
of  higher  oxides,  the  product  was  less  active,  while,  at  the  same  time, 
compounds  containing  even  higher  proportions  of  metallic  nickel  than 
that  first  specified  above,  viz.,  Ni9.30,were  still  less  active  than  the  latter." 

Boron  may  be  used  as  a  catalyzer  according  to  Hildesheimer.*  If 
the  material  is  a  gas  it  is  simply  mixed  with  hydrogen  and  passed  over 
the  boron  material;  if  liquid,  it  is  mixed  with  boron  and  hydrogen  is 
passed  through  it.  When  the  addition  of  hydrogen  is  completed  the 
boron  is  separated  by  filtration  and  is  ready  for  use  again.  The 
catalytic  action  is  assumed  to  depend  upon  the  intermediate  forma- 
tion of  boron  hydride  BH3.  The  rate  of  conversion  is  influenced  by 
the  temperature  and  pressure  as  well  as  the  amount  of  boron.  Cotton- 
seed oil  and  other  unsaturated  compounds,  such,  for  example,  as  ethyl- 

*  Zeitsch.  f.  angew.  Chem.  (1913),  Ref.  583. 


144 


THE  HYDROGENATION  OF  OILS 


ene,  add  hydrogen  under  these  conditions.  In  place  of  boron  some 
of  its  compounds,  such  as  boron  hydride,  and  metallic  compounds  of 
boron,  such  as  aluminium  boride,  may  be  used.  Gases  containing 
hydrogen  may  be  used  in  place  of  pure  hydrogen.* 

On  the  large  scale  the  manufacture  of  catalyzers  by  reduction  of  the 
oxide  of  a  metal  in  a  current  of  hydrogen  has  been  found  to  bring  with 
it  a  train  of  difficulties.  A  method  of  reducing  catalyzer  in  a  con- 
tinuous manner  f  which  simplifies  the  operation  to  a  considerable 
extent  is  shown  in  Fig.  46.  A  charge  of  the  material  to  be  reduced 


FIG.  46. 

is  fed  from  the  hopper  and  feed  arrangement  into  a  series  of  hori- 
zontal parallel  conveyors  1,  2,  3  and  4  into  which  a  current  of  hydrogen 
gas  is  introduced  by  the  pipe  5.  These  conveyors  connect  one  with 
another  alternately  so  that  the  material  travels  in  one  direction  through 
a  given  conveyor,  then  falls  into  the  conveyor  beneath  and  travels  in 

*  A  process  of  hydrogenation  involving  the  use  of  chloride  of  mercury  is  described 
in  an  Austrian  patent  application  noted  in  Seifen.  Ztg.  (1913),  1413.  According  to 
the  method  set  forth  fatty  acids  or  their  glycerides  are  heated  to  a  temperature 
below  180°  C.  with  a  mixture  of  a  difficultly  reducible  inorganic  salt  of  a  base  metal 
in  company  with  chloride  of  mercury  and  at  the  same  time  hydrogen  or  other  reduc- 
ing-gas  mixture  is  passed  through  the  oil. 

t  Ellis,  U.  S.  Patent  1,078,541,  Nov.  11,  1913. 


THE  BASE  METALS  AS  CATALYZERS 


145 


an  opposite  direction.  At  the  same  time  the  material  is  heated  to  the 
proper  temperature  of  reduction  and  throughout  its  travel  is  in  con- 
tact with  a  counter-current  of  hydrogen.  Thus,  the  more  nearly 
reduced  material  is  constantly  progressing  into  a  zone  of  purer  hydro- 
gen, while  the  fresh  raw  material  meets  hydrogen  charged  with  steam. 
In  this  manner  conditions  of  reduction  are  so  facilitated  that  the  use 


FIG.  47. 


of  a  great  excess  of  hydrogen  to  remove  the  steam  does  not  become 
necessary.  After  the  catalyzer  has  been  reduced  it  may  be  mixed 
with  oil  in  another  conveyor  and  be  subsequently  carried  to  a  grinder 
or  beating  apparatus  where  the  coarser  particles  are  broken  down. 

Another  form  of  catalyzer  reducing  chamber  is  shown  in  Fig.  47 
and  consists  of  a  closed  chamber  equipped  with  a  stirrer  and  with  a 
conveyor  to  remove  the  reduced  material.* 


Ellis,  U.  S.  Patent  1,084,202,  Jan.  13,  1914. 


CHAPTER  VI 
THE  BASE  METALS  AS  CATALYZERS— Continued 

Dewar  and  Liebmann  *  observe  that  the  temperature  at  which  the 
reduction  by  hydrogen  of  oxides  or  hydrates  of  nickel,  cobalt,  copper 
and  iron  commences  can  be  considerably  reduced  and  that  this  is 
of  importance  as  the  production  of  catalysts  at  a  low  temperature 
is  advantageous. 

The  lower  temperature  prevents  the  possibility  of  the  new  molecular  aggre- 
gations of  the  finely-divided  metals.  It  renders  it  possible  to  produce  the 
catalyst  and  effect  hydrogenation  in  one  operation,  at  such  a  low  temperature 
as  prevents  decomposition  of  the  oils  and  fats.  The  method  of  Dewar  and 
Liebmann  consists  in  the  reduction  by  hydrogen  at  a  relatively  low  temperature 
of  a  mixture  of  the  oxides  or  carbonates  (either  hydrated  or  anhydrous)  of  two 
or  more  catalytic  metals,  Ni,  Co,  Cu  and  Fe,  or  of  a  mixture  of  the  oxides  of 
one  or  more  of  these  catalytic  metals  with  palladium,  platinum  or  silver  in  a 
fine  state  of  division.  A  mixture  of  the  oxides  of  one  or  more  of  these  catalytic 
metals  along  with  silver  oxide  can  also  be  employed.  A  mixture  of  anhydrous 
oxides  may  be  obtained  from  the  hydrates  or  nitrates  or  carbonates  by  heating. 
In  practice  they  find  that  in  preparing  the  anhydrous  oxides  from  a  mixture  of 
nitrates,  the  use  of  a  mixed  aqueous  solution  gives  on  evaporation  a  product 
which,  after  heating,  is  particularly  suitable  for  the  reduction. 

The  following  examples  are  given  by  Dewar  and  Liebmann: 

(1)  A  solution  prepared  by  dissolving  98.2  parts  of  nickel  nitrate  (6Kf2O)  and 
9.3  parts  of  copper  nitrate  (6H2O)  is  heated  and  precipitated  while  hot  with  a 
slight  excess  of  caustic  soda.     The   mixture  is  then  boiled  and  the  precipitate 
collected  on  a  filter  and  washed  with  hot  water  until  free  from  soluble  salts.     It 
is  subsequently  dried  on  the  water-bath  and    the  drying  is  finally  completed  in 
an  oven  at  a  tempercture  of  about  130°  C.     The  reduction  by  hydrogen  is  nearly 
completed  after  about  two  hours  at  about  170°  C. 

(2)  A  solution    prepared  by  dissolving  44.6  parts  of  cobalt  nitrate   (crystals) 
and  4.65  parts  of  copper  nitrate    (crystals)   is  heated  and  precipitated  with  a 
slight  excess  of  caustic  soda.     The  mixture  is  then  boiled  and  the  precipitate 
collected  on  a  filter  and  washed  with  hot  water  until  free  from  soluble  com- 
pounds, then  dried  on  the  water-bath.     The  reduction  by  hydrogen  is  practically 
complete   after  four  hours   at   about    180°   C.     The  reduction   product   contains 
10  per  cent  copper  and  90  per  cent  of  cobalt. 

(3)  A  solution  prepared  by  dissolving  65  parts  of  iron  nitrate  (crystals)  and 
4.65   parts   of   copper   nitrate    (crystals)    is   heated   and   precipitated   while   hot 
with  a  slight  excess  of  caustic  soda.     The  mixture  is  boiled,  filtered   and  washed 

*J.  S.  C.  I.,  1914,  797,  British  Patent  No.  12,981,  1913;  U.S.  Patent  No. 
1,268,692,  June  4,  1918.  See  also  U.  S.  Patent  No.  1,156,068,  Oct.  12,  1915  to  Ellis. 

146 


L*          £/J.V/Vt< 

>K(O)  a 


THE  BASE   METALS  AS  CATALYZERS  147 

until  free  from  soluble  compounds,  then  subsequently  dried  on  the  water-bath. 
The  reduction  by  hydrogen  is  practically  complete  after  two  and  one-half  hours 
at  from  about  275°  to  320°  C.  The  reduction  product  contains  10  per  cent  of 
copper  and  90  per  cent  of  iron. 

(4)  A  solution  of   .218  part  of   platinum  chloride    and  49.1    parts  of  nickel 
nitrate    (crystals)   is  poured  into  a  boiling  aqueous    solution    containing    thirty 
parts  of  caustic  soda  and  two  parts  by  weight  of  40  per  cent  formalin.     The 
boiling  is  continued  for  some  time  and  the  precipitate  separated  is  collected  on  a 
filter,  washed  until  free  from  soluble  salts    and  dried  on  the  water-bath.     On 
being  treated  with  hydrogen,   the  reduction  is  practically  complete  after  four 
hours  at  about  200°  C.  and  the  reduction  product  contains  1  per  cent   of   plat- 
inum and  99  per  cent  nickel.     Mixtures  of  nickel  hydrate  and  palladium  can  be 
prepared  in  like  manner. 

(5)  A  solution  of  89.2  parts  of  nickel  nitrate  (crystals)  and  3.16  parts  of  silver 
nitrate  is  poured  into  a  warm  solution  of  30  parts  of  caustic  soda  and  boiled. 
The   precipitate   is  then   collected  on  a  filter,   washed    until  free  from  soluble 
compounds  and  dried  on    the  water-bath.     The  reduction  of  this  compound  by 
hydrogen  is  practically  complete  in  about  two  hours  at  about  200°  to  210°  C. 
and   the   reduction   product   contains   10  per   cent  of  silver  and  90  per  cent  of 
nickel. 

(6)  Forty-two  parts  of  kieselguhr  are  impregnated  with  100  parts  of  a  solution 
containing  12^  parts  of  nickel  nitrate  (crystals)  and  12|  parts  of  copper  nitrate 
(crystals).     A  solution  of  11  parts  of  sodium  carbonate  in  100  parts  of  water  is 
added  and  the  whole  well  stirred  together.     The  precipitate  is  collected  on  a 
filter,  washed  thoroughly  until  free  from  soluble  salts  and  dried  on  the  water- 
bath.     The  reduction   is  practically   complete   after  one  hour's  treatment  with 
hydrogen  at  about  170°  C.,  and  the  reduction  product  contains  after  treatment 
for  another  hour  at  about  180°  C.  99  per  cent  of  metallic  contents. 

A  metal  powder  catalyzer  is  prepared  by  Ellis*  by  reducing  nickel 
hydrate  suspended  in  heated  oil  through  which  hydrogen  is  passed. 
Composite  catalyzers  such  as  nickel  and  cobalt  or  copper  are  pre- 
pared in  a  similar  manner.  The  nickel-copper  catalyzer  is  useful  in 
hydrogenating  fish  oil.  It  also  has  been  found  more  active  than  nickel 
alone  in  hydrogenating  oleic  acid. 

Kay  serf  refers  to  the  use  in  catalytic  processes,  of  nickel  com- 
pounds, such  as  the  carbonate,  hydrate,  oxide,  formate  or  acetate 
and  notes  that  before  these  bodies  become  capable  of  transmitting 
hydrogen,  they  have  to  suffer  preliminary  changes,  of  a  hitherto 
undefined  nature.  Such  changes,  he  claims,  do  not  take  place  at  a 
temperature  materially  below  250  or  even  275°  C.  Once  formed,  the 
catalyzers  will  transmit  hydrogen  to  fatty  bodies  at  a  more  moder- 
ate temperature. 

Excessive  heating  of  all  but  a  limited  quantity  of  fatty  material  may  be 
avoided,  in  the  practice  of  fat-hardening,  by  preparing  a  concentrated  fatty 

*U.  S.  Patent  No.  1,156,068,  October  12,  1915. 
t  U.  S.,  Patent  No.  1,236,446,  August  14,  1917. 


148  THE  HYDROGENATION  OF  OILS 

catalyzer-paste  or  catalyzer-cake,  which  is  thereafter  used  at  a  lower  tempera- 
ture for  the  conversion  of  unsaturated  fatty  bodies  in  presence  of  hydrogen; 
or  the  preliminary  treatment  of  the  catalyzer  stock  may  be  carried  out  at  rela- 
tively high  temperatures  in  another  medium,  such  as  paraffine  wax,  the  resulting 
catalyzer  being  thereafter  isolated.  These  methods,  however,  are  stated  to  be 
not  without  inconvenience  and  drawbacks.  Kayser  observes  that  these  nickel 
compounds,  and  some  others  not  hitherto  available,  can  readily  be  converted 
into  catalyzers  of  superior  activity  and  longevity,  and  this  at  a  temperature 
not  exceeding  180°  C.,  when  the  preliminary  treatment  is  carried  out  in  presence 
of  a  small  quantity  of  certain  finely-divided  metals,  and  that  fatty  bodies  can, 
at  a  moderate  temperature,  be  conveniently  saturated  with  hydrogen  to  any 
desired  degree  if  they  are  submitted  to  the  action  of  hydrogen  in  the  simul- 
taneous presence  of  the  usual  amount  of  nickel  compound  and  of  a  compara- 
tively small  amount  of  finely-divided  auxiliary  catalytic  metal,  such  as  would  by 
itself  exercise  upon  the  fat  but  very  slight  action,  or  no  action  whatever. 

Thus,  if  cottonseed  oil  be  agitated  with  hydrogen  at  180°  C.  in  presence  of 
about  2.5  per  cent  of  commercial  nickel  carbonate,  the  mixture  does  not  change 
color,  and  no  hardening  of  the  oil  takes  place.  If  the  oil  be  similarly  reated 
with  gas  in  the  sole  presence  of  about  |  g.  of  so-called  "  atomic  "  copper,  pre- 
pared by  the  action  of  zinc  dust  on  copper  sulphate  solution,  a  like  negative 
result  is  registered.  If,  however,  quantities  of  nickel  carbonate  and  copper  metal 
be  simultaneously  present,  the  charge  rapidly  darkens  and  becomes  progressively 
hardened,  showing  after  two  hours  a  melting-point  of  46°  C.,  after  three  hours, 
52°  C.,  and  after  four  hours,  56°  C.  When  finally  freed  from  suspended  cata- 
lyzer by  filtration  or  other  mechanical  means,  the  fat  will  set  to  a  white,  taste- 
less and  odorless,  brittle  solid.  The  recovered  catalyzer  can  repeatedly  be  used 
in  the  same  manner;  its  activity  will  at  first  be  found  to  increase  and  then  to 
slowly  decline.  Similar,  but  somewhat  inferior,  results  are  stated  to  be  pro- 
duced with  nickel  hydrate  in  place  of  carbonate,  while  the  oxides  and  organic 
nickel  salts  do  not  readily  cooperate,  or  entirely  fail,  with  copper.  Such  organic 
compounds,  as  the  formate,  on  the  contrary  are,  like  the  hydrate,  the  carbonate 
and  the  oxide  of  nickel,  rapidly  transformed  and  activated  by  a  small  quantity 
of  catalytic  metallic  nickel,  produced  by  dry  reduction  of  the  oxide,  hydrate  or 
carbonate  in  a  current  of  hydrogen.  Even  the  oxalate,  otherwise  quite  stable, 
at  275°  C.  is  said  to  be  readily  transformed  into  an  efficient  catalyzer.  For 
example,  250  g.  of  cottonseed  oil,  agitated  with  hydrogen  at  180°  C.  in  presence 
of  3.5.  g.  of  active  nickel-powder,  are  in  three  hours  hardened  to  a  melting-point 
of  37°  C.;  in  the  simultaneous  presence  of  7  g.  of  nickel  hydrate  the  charge 
rapidly  turns  grey  and,  when  filtered  after  three  hours  running  yields  a  white  fat, 
melting  at  54°  C.  In  the  same  manner,  cooperation  of  0.5  g.  nickel-powder  with 
12.5  g.  nickel  oxalate  yields  in  three  hours  a  white  fat,  melting  at  54°  C.  The 
reactions  described  may  frequently  be  facilitated  by  using,  instead  of  the  pure 
nickel  compound  and  the  pure  auxiliary  metal,  the  like  bodies,  deposited  upon 
kieselguhr  or  a  similar  indifferent  support.  The  chemical  nature  and  the  appear- 
ance of  the  catalyzer  produced  by  the  process,  varies  with  the  auxiliary  metal 
employed.  Nickel  is  stated  to  yield  a  grey,  non-metallic  catalyzer,  while  copper 
produces  a  black  body,  developing  with  hydrochloric  acid  far  less  hydrogen, 
than  what  would  correspond  with  the  hypothetical  sub-oxide  Ni2O. 

A  catalyzer  used  by  Lubeck  and  Payet*  is  prepared  by  mixing  cuprous  chloride 
*J.  S.  C.  I.,  1909,  830.  French  Patent  No.  397,746,  March  5,  1908. 


THE  BASE  METALS  AS  CATALYZERS  149 

with  native  hydratcd  cobalt  oxide  and  heating  in  vacuo  to  450°  C.  A  current 
of  hydrogen  or  of  illuminating  gas,  previously  heated  to  120°  C.,  is  then  passed 
over  the  material.  By  treatment  with  hydrochloric  acid  cuprous  chloride  is 
dissolved  and  a  double  chloride  of  cobalt  and  copper  precipitated,  or  a  mixture 
of  hydrated  cobalt  chloride  and  copper  chlorides,  according  to  the  conditions 
of  heating  in1  hydrogen.  The  precipitate  is  allowed  to  settle  on  pieces  of  pumice 
which  are  afterwards  dried. 

Silicious  material,  known  as  monox  or  silicon  monoxide,  which  is 
of  a  very  light  and  voluminous  character  and  is  prepared  in  an 
electric  furnace  was  tested  in  the  author's  laboratory  as  a  support- 
ing material  for  nickel  in  the  preparation  of  a  catalyzer. 

By  means  of  a  solution  of  nickel  nitrate  the  monox  was  saturated  with  the 
nickel  solution  and  the  mixture  ignited  until  red  fumes  ceased  to  be  evolved. 
The  product  was  then  reduced  to  a  fine  powder  and  heated  for  one  hour  in  a 
current  of  hydrogen  at  a  temperature  of  340°  C.  The  reduced  catalyzer  was 
preserved  under  oil.  The  proportions  used  in  preparing  the  materials  were 
10  parts  by  weight  of  nickel  nitrate  Ni(NOl-)2-6H2O  to  8  parts  of  monox. 
Cottonseed  oil  containing  5  per  cent  of  this  catalyzer  or  approximately  1  per 
cent  of  the  reduced  nickel  was  heated  for  3^  hours  to  174°-189°  C.,  while  a 
continuous  stream  of  hydrogen  was  passed  through  the  oil  and  the  melting- 
point  of  the  hardened  product  which  resulted  was  48.2°  C. 

Fresenius  describes  a  process  of  hydrogenating  organic  compounds 
such  as  unsaturated  oils  which  consists  in  mixing  the  oil  with  pure 
powdered  carbon  (Kohlenpulver)  heating  and  conducting  in  the 
presence  of  hydrogen  over  contact  material  such  as  porous  carbon, 
metal  carbides  or  other  known  contact  materials.  The  hydrogena- 
tion  is  in  this  manner  carried  to  completion  in  a  short  time.  Fur- 
thermore, this  process  is  stated  to  avoid  high  temperatures  common 
to  other  processes  so  that  the  fat  is  not  injured  and  hence  the  product 
is  well  adapted  for  edible  purposes.  *f 

A  method  of  preparation  of  a  nickel-charcoal  catalyzer  is  described 
by  Ellis,  t 

The  charcoal  may  be  purified  by  washing  with  dilute  nitric  acid  and  also  in 
some  cases  with  alkali  so  as  to  remove  undesirable  mineral  matter;  finally 
washing  with  distilled  water,  thereby  obtaining  a  good,  clean  material.  Nickel 
hydroxide,  preferably  freshly  prepared  in  a  state  of  purity  is  dissolved  in  a  con- 
centrated ammoniacal  solution  and  the  charcoal  is  treated  with  the  solution. 
Only  approximately  enough  ammonia  is  used  to  dissolve  the  nickel  hydrate  and 
the  quantity  of  the  latter  with  reference  to  the  amount  of  the  charcoal  is  prefer- 

*Seifen.  Ztg.,   1914,   1282. 

t  The  use  as  catalyzers  of  such  substances  as  iron  oxide,  pumice  stene,  bone  black, 
charcoal  or  copper  oxide  is  recommended  by  Ellis  and  McElroy  (U.  S.  Patent  No. 
914,251  of  March  2,  1909),  in  connection  with  the  manufacture  of  chlorinated  naph- 
thalene. 

JU.  S.  Patent  No.  1,156,674,  October  12,  1915. 


150  THE  HYDROGENATION  OF  OILS 

ably  proportioned  to  give  a  product  having  from  10  to  30  per  cent  of  nickel. 
After  the  nickel  solution  and  the  charcoal  have  been  incorporated  the  material 
is  dried  when  the  ammonia  evaporates  and  the  product  is  then  reduced  with 
hydrogen.*  f 

A  catalyzer,  for  hydrogenating  oils,  described  by  Ittner  t  is  pre- 
pared frcm  charcoal  which  has  deposited  throughout  its  structure  a 
small  amount  of  certain  mineral  bodies,  as,  for  example,  compounds 
of  the  earth  metals  or  alkaline  earth  metals,  such  as  alumina,  or 
silicates  of  metals  like  aluminum,  calcium,  magnesium  and  cerium. 

The  product  is  stated  to  possess  entirely  different  properties  from  ordinary 
charcoal,  in  so  far  as  its  catalytic  activity  is  concerned,  although  in  other  respects 
identical  with  ordinary  charcoal.  Ittner  observes  that  this  superior  catalytic 
activity  of  the  charcoal  treated  as  described  is  developed  when  it  is  used  as 
the  porous  body  upon  which  catalytic  material,  e.g.,  metallic  nickel,  active  nickel 
oxide,  or  the  like,  is  deposited,  and  is  extraordinary  in  degree.  In  the  prepara- 
tion of  the  charcoal  spruce  or  cedar  wood  may  be  subjected  to  dry  distillation  in 
a  retort.  Good  results  are  obtained  with  both  coniferous  and  deciduous  wood. 
Active  charcoal  also  may  be  made  from  other  organic  substances,  as,  for  instance, 
cornstalks  and  peat.  The  atmosphere  of  the  retort  may  be  kept  under  reduced 
pressure,  or  the  distilling  operation  may  be  expedited  by  means  of  a  current 
of  superheated  steam  passed  through  the  retort,  or  a  current  of  carbon  dioxide 
gas.  It  is  best  not  to  use  too  high  a  temperature  in  making  the  charcoal,  but 
it  should  nevertheless  be  sufficiently  high  to  drive  off  volatile  matter.  After 
the  distillation  has  progressed  until  volatile  products  of  decomposition  are  no 
longer  given  off  by  increased  heat,  the  resulting  charcoal  is  allowed  to  cool  out 
of  contact  with  the  air.  When  cool,  it  may  then  be  powdered,  and  saturated 
with  a  dilute  solution  of  an  alkaline  silicate;  an  8  per  cent  solution  of  sodium 
silicate  may  be  used  to  advantage.  The  charcoal  thus  impregnated  with  silicate 
should  then  be  heated  in  a  closed  retort,  to  a  dull  red  heat  or  a  temperature 
somewhat  under  a  dull  red  heat.  It  should  then  be  allowed  to  cool  to  atmos- 
pheric temperature  out  of  contact  with  air  before  being  removed  from  the  retort 
and  may  then  be  treated  with  a  solution  of,  say,  aluminum  sulphate,  alum,  or 
other  salt  of  aluminum.  The  support  thus  prepared  may  be  washed  with  water, 
and  coated  or  impregnated  with  catalytic  metal,  as  for  instance,  nickel,  or  the 
active  oxide.  Any  of  the  well-known  methods  for  coating  or  impregnating  a 
support  with  an  active  catalytic  metal  may  be  used.  If  the  nickel  is  obtained 
by  first  saturating  the  active  charcoal  with  a  solution  of  nickel  nitrate,  and 
later  igniting  in  the  presence  of  the  nitrate,  a  dilute  solution  of  the  nitrate  is 
found  to  give  the  best  results.  A  good  way  to  prepare  the  catalyzer  is  to  sat- 
urate the  active  charcoal  with  a  solution  of  some  nickel  salt,  remove  the  excess 
nickel  solution  by  pressure  or  filtration,  and  then  treat  the  active  charcoal, 
coated  and  impregnated  with  nickel  solution,  with  an  excess  of  a  dilute  solution 
of  sodium  carbonate  or  other  precipitant,  whereby,  Ittner  states,  the  nickel 
becomes  fixed  within  and  upon  the  active  charcoal  in  a  form  insoluble  in  water. 

*  Finely-divided    nascent   carbon   which    forms   in    cracking   oils   acts   as    a    hydro- 
genating catalyst  under  some  conditions  (British  Patent  No.  9,728,  July  3,  1915.) 
fSee  also  U.  S.  Patent  No.  1.174,245,  March  7,  1916  to  Ellis. 
JU.  S.  Patent  No.  1,238,774,  September  4,  1917. 


THE  BASE  METALS  AS  CATALYZERS  151 

The  excess  sodium  carbonate  and  other  soluble  salts  should  then  be  washed 
out  with  water,  and  the  mass  subjected  to  drying  and  to  heat  in  a  current  of 
hydrogen  gas  to  yield  metallic  nickel.  Ittner  also  gives  directions  for  making 
nickel  oxide  hi  active  form,  in  place  of  the  metal.  A  catalyzer  prepared,  as 
described,  from  charcoal  rendered  active  by  the  treatment  noted  is  asserted  to  be 
from  ten  to  more  than  one  hundred  times  as  active  in  the  hydrogenation  of  oils 
as  a  catalyzer  which  is  in  all  other  respects  the  same  except  for  the  manner  in 
which  the  charcoal  is  prepared,  and  it  is  very  much  more  active  than  catalyzers 
in  other  respects  the  same  but  which  are  made  with  the  employment  of  kiesel- 
guhr,  pumice,  or  other  inert  porous  suppon  in  place  of  active  charcoal. 

A  method  of  forming  a  catalyzer  described  by  Tamari*  is  as  follows: 
A  suitable  reagent  is  added  to  a  solution  of  such  composition  that 
not  only  the  catalyzer  is  precipitated,  but  also  a  difficultly  soluble 
carrier  for  the  same,  either  simultaneously  or  consecutively.  This 
procedure  permits  (1)  the  uniform  distribution  of  the  catalyzer  in  a 
finely-divided  state  over  the  carrier,  (2)  a  ready  control  of  the  dis- 
tribution of  the  catalyzer,  (3)  determination  of  the  specific  gravity 
of  the  catalytic  product  by  the  proper  choice  of  the  amount  and 
character  of  the  carrier,  so  that  when  it  is  used  in  a  liquid  medium 
it  will  float  or  sink  or  remain  in  suspension,  as  desired,  and  (4) 
the  removal  of  moisture,  when  necessary,  by  the  selection  of  an 
absorbent  carrier;  calcium  sulphate  and  alumina  being  mentioned 
for  the  purpose. 

A  catalyzer  adapted  for  use  in  the  production  of  light  from  heavy 
hydrocarbons  is  recommended  by  Valpy  and  Lucas,  f  In  its  prepara- 
tion a  powdered  metallic  oxide  or  a  mixture  of  oxides  is  heated  with 
organic  compounds  oi  the  metal. 

Suitable  proportions  for  a  catalyzer  for  the  production  of  light  hydrocarbons 
from,  heavy  hydrocarbons  are:  Ferric  oxide,  32;  nickel  oxide,  7.5;  carbon,  5.5; 
ferrous  oxalate,  40;  and  nickel  oxalate,  15  parts.  The  mixture  is  incorporated 
with  17£  per  cent  by  weight  of  tar,  briquetted,  and  sintered  in  an  enclosed 
crucible  to  effect  reduction,  at  a  temperature  below  the  melting-point  of  the 
metal.  The  procedure  may  be  applied  to  other  catalytic  metals,  e.g.,  chromium, 
cobalt,  or  manganese.  The  addition  of  small  amounts  of  aluminum,  cerium, 
magnesium,  or  other  members  of  the  alkaline  earth  group  is  an  advantage  in 
many  cases,  for  example,  a  portion  of  the  carbon  may  be  replaced  by  powdered 
aluminum  to  the  extent  of  1.5  per  cent  of  the  total  weight  of  the  mixed  powder. 
Other  suitable  mixtures  are:  (1)  Ferric  oxide,  35;  manganese  carbonate,  27; 
carbon,  3;  aluminum,  5;  and  ferrous  oxalate,  30  parts.  (2)  Ferric  oxide,  36; 
nickel  oxide,  15;  aluminum,  3;  iron  tartrate,  30;  and  nickel  acetate,  16  parts. 
17.5  parts  of  tar  are  used  in  each  case.  The  catalytic  bodies  so  obtained  do  not 
appear  to  lose  their  effectiveness  after  continued  use;  in  fact  in  some  cases  an 
increase  in  efficiency  after  a  short  period  of  use  lias  been  observed. 

*  Japanese  Patent  No.  29,986,  September  5,  1916;    Chem.  Abs.,  1917,  529. 
t  British  Patent  No.  5847,  March  7,  1914;    J.  S.  C.  I.,  1915,  784. 


152  THE  HYDROGENATION  OF  OILS 

The  Badische  Co.*  report  that  the  hydrogenation  and  dehydrogen- 
ation  of  compounds  containing  carbon  can  be  carried  out  rapidly 
and  at  comparatively  low  temperatures,  by  employing,  as  the  cata- 
lytic agent,  an  intimate  mixture  of  either  iron,  nickel,  cobalt,  or 
copper,  with  a  high  melting  and  difficultly  reducible  oxide,  in  par- 
ticular, the  oxides  and  oxygen  salts  of  the  earth  metals,  including 
the  rare  earths,  and  those  of  beryllium,  magnesium,  manganese, 
uranium,  vanadium,  niobium,  tantalum,  chromium,  boron,  titanium 
and  also  difficultly  soluble  phosphates,  molybdates,  tungstates  and 
selenates  of  the  alkaline  earths,  and  of  lithium,  or  the  reduction 
products,  containing  oxygen,  of  these  phosphates,  molybdates, 
tungstates,  or  selenates,  as  for  instance,  the  corresponding  selenites. 
All  of  these  compounds  containing  oxygen,  which  augment  the 
activity  of  the  catalytic  agent,  are  termed  "  promoters." 

The  oxygen-containing  salts  of  the  alkaline  earths  and  of  lithium  appear  to 
have  the  same  action  as  the  corresponding  salts  of  aluminum,  magnesium,  and 
the  like,  although  lithium  oxide  and  the  oxides  of  calcium,  barium,  and  stron- 
tium, are  themselves  not  suitable  for  use  as  promoters. 

An  intimate  mixture  of  the  catalytic  metal  and  a  promoter  is  required  and  it 
is  not  sufficient,  according  to  the  Badische  Co.,  merely  to  pack  the  components, 
for  instance,  nickel  and  alumina,  side  by  side,  into  the  reaction  space,  nor  is  it 
adequate  to  absorb  a  solution  of  a  salt  of  the  catalytic  metal  into  a  porous  mass, 
such  as  magnesia,  and  then  decompose  the  salt  of  the  catalytic  metal.  Good 
results  can  be  obtained  by  precipitating  the  hydroxides,  oxides,  or  carbonates,  of 
the  components;  or  mixtures  of  salts,  for  instance,  the  nitrates  of  the  com- 
ponents, can  be  heated  to  fusion.  Further,  it  is  stated  that  the  mixture  can  be 
obtained,  although  not  always  with  equal  certainty  and  excellence,  by  mechan- 
ical operations,  such  as  by  grinding  together  as  finely  as  possible,  or  by  kneading 
in  a  moist  state.  If  necessary  the  mixture  is  subsequently  heated  and  reduced 
so  that  the  catalytic  metal  (iron,  nickel,  cobalt,  or  copper),  is  obtained  in  a  metallic 
condition,  while  the  promoter  always  retains  more  or  less  oxygen.  When  the  pro- 
moter is  to  consist  of  an  insoluble  oxide  such,  for  instance,  as  aluminum  oxide  and 
titanium  oxide,  it  is  preferred  to  start  with  a  soluble  compound,  and  to  precip- 
itate, or  otherwise  form  the  insoluble  oxide  on  the  catalytic  metal,  or  on  the 
compound  from  which  the  catalytic  metal  is  to  be  prepared.  For  instance,  if 
aluminum  acetate  be  employed  to  yield  the  promoter,  aluminum  oxide,  the  ace- 
tate can  be  merely  heated  in  the  presence  of  the  catalytic  metal,  or  a  compound 
of  the  latter,  so  that  the  acetic  acid  is  driven  off,  and  the  alumina  remains.  If 
insoluble  salts,  such  for  instance,  as  certain  chromates,  and  borates,  be  employed 
as  promoters,  these  are  preferably  brought  into  intimate  mixture  with  the 
compound,  which  is  subsequently  to  give  rise  to  the  metallic  catalytic  agent,  by 
precipitation  from  suitable  soluble  salts.  The  salts  which  act  as  promoters  may 
contain  the  oxide,  to  which  the  promoting  action  is  ascribed,  either  in  the  acid 
constituent,  or  in  the  basic  constituent,  or  in  both  the  acid  and  basic  con- 
stituents. Calcium  aluminate,  and  aluminum  phosphate,  are  instances  of  com- 

*  British  Patent  No.  2306,  1914. 


THE  BASE  METALS  AS  CATALYZERS  153 

pounds  of  this  character.  In  some  cases,  the  promoter  may  consist  of  a  salt, 
of  which  neither  the  acid  constituent,  not  the  basic  constituent  of  itself  acts  as 
a  promoter.  Calcium  phosphate  is  an  example  of  this  type. 

It  is  particularly  advantageous  for  the  purpose  of  producing  a  very  active 
contact  mass  to  prepare,  at  least  the  catalytic  metal,  from  carbonaceous  salts,  or 
mixtures  of  salts;  for  instance  from  carbonates,  or  from  formates.  Sometimes 
the  action  of  the  catalytic  mixture,  it  is  alleged,  can  further  be  increased  by 
adding  an  alkaline  metal  compound,  for  instance,  caustic  soda,  even  traces  of 
such  bodies  often  having  a  favorable  action.  The  introduction  of  bodies  such 
as  chlorine,  sulphur,  arsenic,  and  lead,  which  may,  in  the  elementary  form,  act 
as  contact  poisons,  is  to  be  avoided,  although  these  contact  mixtures  are  claimed 
to  be  not  so  sensitive  to  the  action  of  poisons  as  are  the  pure  metals.  It  is 
consequently  possible  to  employ  as  a  promoter,  an  oxygen  salt  which  contains 
one  of  the  poisonous  elements,  but  in  which  the  poisonous  action  is  counteracted 
by  the  promoting  influence  of  the  oxide;  for  instance,  basic  aluminum  sulphate 
is  observed  to  possess  a  strong  promoting  action.  The  proportion  of  the  com- 
ponents employed  in  the  catalytic  mixture  may  be  varied  considerably,  even  an 
addition  of  1  per  cent,  or  less,  of  the  promoter  is  stated  to  produce  in  most 
cases,  favorable  action.  These  catalytic  mixtures  can  be  used  for  the  hydro- 
genation  and  dehydrogenation  of  compounds  containing  carbon  and  are  claimed 
to  be  of  particular  value  for  the  hardening  of  fats  and  fatty  acids,  but  they  can 
also  be  used  for  other  purposes,  for  instance,  for  converting  phenol  into  cyclo- 
hexanol  and  for  reducing  nitrobenzene  to  aniline,  and  for  the  conversion  of  oxides 
of  carbon  into  hydrocarbons. 

The  use  of  mixtures  containing  strongly  basic  bodies  in  the  hydrogenation  of 
ats  is  undesirable.  The  presence  of  strong  bases  is,  in  such  cases,  detrimental, 
since  they  tend  to  saponify  and  very  soon  disappear  from  the  contact  mass. 

The  following  are  examples  of  how  catalysts  can  be  prepared  according  to 
the  foregoing,  and  how  they  are  applied  in  the  hydrogenation  of  organic  bodies. 
The  parts  are  by  weight. 

1.  Pour  an  aqueous  solution  of  1  part  aluminum  nitrate  over  5  parts  of  nickel 
oxalate,  evaporate  the  mixture  and  dry  it  and  reduce  it  in  a  current  of  hydro- 
gen at  from  300°  to  350°  C.     Then  introduce  the  catalyzer,  while  excluding  air, 
into  a  vessel,  provided  with  a  stirrer,  the  vessel  containing  fish  oil.     On  treat- 
ment with  hydrogen  at,  for  instance,   100°  C.,  hydrogenation  takes  place  con- 
siderably more  rapidly  than  if  pure  nickel  were  employed  as  the  catalytic  agent. 
Instead  of  aluminum  nitrate,  cerium  nitrate,  or  cerium  ammonium  nitrate,  can 
be  employed. 

2.  Precipitate  a  hot  solution  containing  nickel  nitrate  and  aluminum  nitrate 
with  potassium  carbonate,  wash  and  dry  the  precipitate,  heat  it  to  300°  C.,  and 
reduce  with  hydrogen.     Then  place  the  catalytic  mixture  with  soya  bean  oil  in 
an  autoclave,  while  avoiding  the  presence  of  air,  heat  to  80°  C.  and  allow  hydro- 
gen to  act  at  a  pressure  of  twenty  atmospheres  while  mixing    the    constituents. 
The  hydrogenation   takes  place   very  rapidly.     If  desired  the   pressure   can   be 
increased,  for   instance,   up  to  fifty   atmospheres,   or  higher.     In   this   example, 
good  results  can  also  be  obtained  if  iron  nitrate  be  employed  instead  of  nickel  nitrate. 

3.  Mix   13  parts  of  nickel  hydroxide  with  2  parts  of  magnesium   hydroxide, 
and   warm   gently   with   concentrated   formic   acid   free   from   sulphur,    until   the 
formates  are  obtained.     Heat  the  mixture  cautiously  until  dry,  and  then  treat 
with  hydrogen  at  300°  C.     On  treating  olive  oil  with  hydrogen  in  the  presence 


154  THE  HYDROGENATION  OF  OILS 

of  this  catalytic  mixture  at  say,  from  80°  to  100°  C.  hydrogenation  is  effected 
more  rapidly  than  is  the  case  when  pure  nickel  is  used.  In  this  example  the 
hydroxides  can,  if  desired,  be  replaced  by  the  corresponding  carbonates.  Car- 
riers such  as  pieces  of  clay  can  be  employed,  these  being  soaked  in  a  melt,  or 
solution,  of  nickel  salts,  preferably  of  the  soluble  double  salts,  such  as  nickel 
ammonium  formate,  or  ammoniacal  nickel  carbonate,  together  with  similar  salts 
of  the  promoter,  and  then  treated  as  described. 

4.  Make  nickel  wire  netting  into  the  form  of  loose  spheres  or  rolls,  clean  these 
with  pure  dilute  nitric  acid,  wash  and  moisten  them  with  a  moderately  concen- 
trated solution  of  aluminum  nitrate;    then  dry  and  treat  with  hydrogen  at  from 
300°   to   350°   C.     The    contact   mass   containing   alumina   can,   for   instance,   be 
employed  for  the  hydrogenation  of  linseed  oil  which  can  be  allowed  to  trickle 
over  the  catalytic  agent  while  the  hydrogen  is  supplied. 

5.  Dissolve  85  parts  of  nickel  nitrate  and   15  parts  of  titanium  lactate  in  a 
small  quantity  of  hot  water  and  precipitate  by  means  of  caustic  soda,  or  sodium 
carbonate,  then  filter,  wash,  dry,  and  reduce  with  hydrogen  at  300°  C.  and  add 
the  catalytic  mixture  containing  titanium  oxide  to  cottonseed  oil,  and  treat  with 
hydrogen   at  from    100°  to    120°   C.,   while   keeping  the   mixture   in   motion.     If 
desired  the  reaction  can  be   carried  out  under  increased  pressure    (for  instance, 
100  atmospheres)   and  in  this  case  the  hydrogenation  takes  place  very  rapidly, 
and  completely,  even  at  a  temperature  of  90°  C.  or  lower.     Further,  the  process 
can  be  made  continuous  by  allowing  the  oil  to  flow  over  the  catalytic  agent  in  a 
vessel  capable  of  withstanding  pressure  while  simultaneously  passing  a  current  of 
hydrogen  into,  or  through  the  apparatus.     The  product  is  drawn  off  while  hot 
and  allowed  to  solidify. 

6.  Take  freshly  precipitated  nickel  carbonate  and  add  from  10  to  20  per  cent 
of  its  weight  of  ammonium  or  potassium  borate,  which  has  previously  been  dis- 
solved in  water.     Then  form  the  mass  into  any  desired  shape,  and  dry  and  reduce 
it.     The  mixture   can  be   employed  for  hydrogenating  oils    and    fats,   either  at 
ordinary  pressure  or  under  increased  pressure.     If  chromium    oxide  be  used  as 
the  promoter,  this  can  be  obtained,  for  instance,  from  chromium  nitrate,  or  from 
soluble    chromates,    by   precipitation.     Further,    when    boron    oxide    is    employed 
as  the  promoter,  the  oxide,  or  carbonate,  of  the  catalytic  metal  may  be  mixed 
with  solid,  or  dissolved,  boric  acid  and  then  be  heated  and  reduced;    or  the  salt 
of  the  catalytic  metal,  for  instance,  the  nitrate,  can  be  mixed  with  the  borate 
of  the  same  metal,  or  of  a  volatile  or  non-volatile  base,  and  the  mixture  is  then 
calcined  and  reduced. 

7.  Add  two  parts  of  dissolved  potassium  aluminate  to  a  solution   containing 
30   parts   of  nickel   nitrate   and    1|   parts   of   calcium  nitrate   and   introduce   the 
whole  into  a  boiling  solution  of  sodium  carbonate.     Then  filter,  wash  well,  dry 
and  reduce.     Or,  add  a  solution  of  1^  parts  of  magnesium  nitrate  to  5  parts  of 
nickel  carbonate,  and  then  add  a  solution  of  £  of  a  part  of  ammonium  phosphate 
and  precipitate   with  caustic   soda,   or   sodium   carbonate,   filter,   wash,    dry   and 
reduce.     The  nickel  catalytic  agent  containing  calcium  aluminate,  or  magnesium 
phosphate,   as  the   case   may  be,   can  be   employed  for  hydrogenation   purposes, 
for  instance,  it  may  be  introduced  into  oil  which  results  from  cracking  petroleum 
residues    and    which    is    rich    in    unsaturated    compounds,    whereupon    hydrogen 
is  allowed  to  react  at  a    temperature    of    100°  C.  and    at    a    pressure  of   eighty 
atmospheres.     The  iodine  number  is  rapidly  reduced  and  at  the  same  time  the 
color  and  unpleasant  odor  diminish. 


THE  BASE   METALS  AS  CATALYZERS  155 

In  a  similar  manner  other  contact  mixtures  can  be  employed,  which  contain 
as  a  promoter,  for  instance,  calcium  vanadate,  barium  chromate,  aluminum 
borate,  barium  tungstatc,  or  lithium  phosphate,  or  the  compounds  which  result 
on  the  reduction  of  these  bodies. 

8.  To  a  hot  solution  of  13  parts  of  nickel  nitrate  and  2  parts  of  chromium 
nitrate,  add  a  hot  solution  containing  6  parts  of  anhydrous   sodium  carbonate. 
Filter  off  the  precipitate,  wash  it  until  the  filtrate  is  free  from  alkali,  then  dry 
and  reduce  it.     With  the  help  of  this  catalytic  agent,  soya  bean  oil  can  be  hydro- 
genized  rapidly  at  a  low  temperature. 

9.  Suspend  40  parts  of  nickel  carbonate  in  a  solution  containing   1   part  of 
ammonium    tungstate    and   then    add    a   solution    of    1    part    of    barium    nitrate, 
filter  off  the  product,  wash  it  well,  dry  and  reduce  it  at  300°  C.     The  product 
can  be  employed,  for  example,  for  hydrogenating  sesame  oil  at  120°  C. 

10.  Mix  to  a  paste  50  parts  of  nickel  carbonate  and  a  solution  of  13  parts  of 
calcium  nitrate  and  then  stir  in  a  solution  of  7  parts  of  ammonium  phosphate. 
Filter  off  the  product,  wash  well,  dry  and  reduce  at  from  300°  to  350°  C.     The 
product  can  be  employed  for  hydrogenating  fish  oil. 

11.  Stir  80  parts  of  nickel  carbonate  into  a  solution  of  2.6  parts  of  strontium 
nitrate,   and  add  a  solution   of  2  parts  of  ammonium  selenite.     Filter  off  the 
product,  wrash  well,  dry  and  reduce.     The  product  can  be  used  for  hydrogenating 
cottonseed  oil.* 

The  effect  of  preparation  of  catalytic  nickel  under  different  condi- 
tions is  discussed  by  Crossley  f  who  reproduces  some  curves  of  hydro- 
genation  derived  from  experiments  made  by  Hehner. 

Nickel  prepared  from  the  hydroxide  or  from  the  nitrate  through  the  oxide  at  250° 
gave  approximately  the  same  results  on  whale  oil,  but  at  180°  C.,  the  nickel  pre- 
pared from  the  nitrate  was  less  acti«o.  Nickel  produced  by  strongly  heating  the 
nitrate  and  reducing  the  resulting  oxide  was  practically  without  effect  on  linseed 
oil  and  nickel  obtained  from  the  sulphate  through  the  hydroxide  (probably  con- 
taining traces  of  sulphur)  was  markedly  less  active  than  carefully  purified  nickel  from 
the  hydroxide.  The  following  example,  from  evidence  handed  into  court  in  the  case 
of  Joseph  Crosfield  and  Sons,  Limited,  v.  Technico-Chemical  Laboratories,  Limited, 
may  be  cited.  The  iodine  value  of  an  oil  was  decreased  from  108.4  to  72.1  by  treat- 
ment with  hydrogen  in  presence  of  nickel  obtained  by  igniting  nickel  carbonate  at 
400°  to  450°,  and  reducing  the  resulting  oxide  with  hydrogen  at  400°  C.  A  speci- 
men of  the  same  oil  had  its  iodine  value  lowered  to  13.2  when  treated  in  presence  of 
nickel  prepared  from  the  carbonate  by  roasting  at  300°  for  five  to  six  minutes,  and 
reducing  the  resulting  oxide  with  hydrogen  at  300°  C.,  for  four  to  five  minutes. 

Bosch,  Mittasch  and  Schneider  J  also  recommend  complex  com- 
pounds of  fluorine  as  activators  for  catalytic  iron,  nickel,  cobalt  or 
copper.  They  give  the  following  example:  Soak  100  parts  of  nickel 

*Seifen.  Ztg.,  1914,  1133;  Zeitsch.  angew.  Chem.,  Referat.,  1915,  220;  German 
Patent  No.  282,782,  December  12,  1913;  Chem.  Ztg.  Rep.,  1915,  155.  Austrian 
Patent,  No.  72,758,  November  25,  1916.  See  also  U.  S.  Patent  No.  1,271,013,  July  2, 
1918. 

t  Pharm.  Soc.  April  21,  1914;  Pharm.  J.,  1914,  92,  604,  637  and  676;  J.  S.  C.  I.,  1914, 
1135. 

t  U.  S.  Patent  No.  1,216,933,  February  20,  1917. 


156 


THE  HYDROGENATION  OF  OILS 


carbonate  in  a  concentrated  solution  of  10  parts  of  sodium  silico- 
fluoride,  then  dry  and  treat  with  hydrogen  at  320°  C.  Introduce 
the  contact  mass  thus  obtained  into  linseed  oil,  while  avoiding  the 
presence  of  air  and  treat  with  hydrogen  at  a  temperature  of  120°  C. 
and  a  pressure  of  ten  atmospheres.  The  reduction,  and  simulta- 
neously the  hardening,  of  the  oil  take  place  very  rapidly. 

Instead  of  sodium  silico-fluoride,  other  silico-fluorides  can  be  em- 
ployed, for  instance,  those  of  aluminum,  calcium,  and  potassium, 
or  other  fluorine  compounds,  as  barium  fluoride,  calcium-boron 
fluoride,  and  potassium-titanium  fluoride,  can  be  used.  Nickel  wire 
netting  can  be  improved  catalytically  by  soaking  it  first  with  dilute 


,  FIG.  47a. 

nitric  acid  and  then  treating  it  with  a  solution  of  ammonium-silico- 
fluoride,  finally  adding  a  small  quantity  of  aluminium  nitrate  and 
drying  and  reducing. 

An  apparatus  employed  by  Kayser  *  for  reducing  metallic  oxides 
with  hydrogen,  is  shown  in  side  elevation  in  Fig.  47a  and  in  vertical 
cross-section  in  Fig.  476.  It  consists  of  a  rotary  drum  supported 
by  hollow  trunnions,  and  provided  with  vanes  for  agitating  the  mate- 
rial. The  latter  is  introduced  through  a  manhole.  A  reducing  gas 
is  introduced  through  one  trunnion  and  escapes  through  the  other. 
Entrained  matter  is  removed  from  the  used  gas  by  a  trap  and  water 
seal.  The  drum  is  heated  from  beneath  by  gas  burners  mounted  on 
a  removable  carriage.  A  jacket  surrounds  the  drum  forming  a 
space  through  which  the  products  of  combustion  pass  to  the  stacks 
at  the  top.  When  the  charge  has  been  reduced,  the  burner  carriage 

*U.  S.  Patent  No.  1,134,745,  April  6,   1915. 


THE  BASE   METALS  AS  CATALYZERS 


157 


is  removed  and  steam  is  blown  around  the  drum  until  the  latter 
has  cooled  somewhat.  Finally  water  is  sprayed  on  the  drum  for  a 
brief  period  and  the  cooled  contents  are  then  removed. 

Morey  and  Craine  *  describe  a  form  of  apparatus  for  making 
catalytic  material  which  comprises  in  its  main  features  an  inclined 
tube  or  conduit  through  which  the  catalytic  raw  material  flows 
downwardly,  either  by  gravity  alone  or  by  gravity  assisted  by  a 


FIG.  476. 

jarring  or  shaking  action,  and  through  which  the  gas  flows  upwardly, 
the  tube  or  conduit  being  heated  in  any  suitable  manner,  for  instance, 
by  direct  flame,  superheated  steam  or  electrical  current. 

In  Fig.  47c  is  shown  a  side  elevation  of  this  apparatus.  10  represents  the 
inclined  tube  in  which  the  material  is  subjected  to  the  action  of  a  reducing  gas, 
and  to  the  upper  end  of  which  the  raw  material  is  supplied  from  a  feed  recep- 
tacle 11  by  a  flexible  pipe  12.  This  inclined  tube  is  supplied  with  gas  from  a 
gas  holder  13  by  means  of  a  flexible  pipe  14  which  is  connected  with  the  lower 
portion  of  the  tube.  The  treated  material  is  discharged  from  the  lower  end  of 
the  latter  into  a  closed  receptable  15  by  a  flexible  pipe  16  without  exposure  to 
the  atmosphere.  The  gas  escapes  from  the  upper  end  of  the  tube  and  is  con- 
ducted by  a  flexible  pipe  17  to  a  scrubbing  apparatus  18  in  which  objectionable 

*U.  S.  Patent  No.  1,167,915,  January  11,  1916. 


158 


THE  HYDROGENATION  OF  OILS 


matters  are  separated  from  the  gas  and  from  which  the  purified  gas  is  returned 
to  the  gas  holder  13,  to  which  fresh  gas  is  supplied  as  may  be  necessary.  Circu- 
lation of  the  gas  through  the  apparatus  is  maintained  by  a  pump  27.  The 
inclined  tube  or  conduit  is  heated  to  a  reducing  temperature.  When  diatoma- 
ceous  earth  impregnated  with  nickel  hydroxide  is  treated,  a  temperature  of  about 
550°  F.  is  preferred.  The  treating  tube  may  be  inclined  at  such  an  angle, 
usually  about  42°,  that  the  material  will  flow  through  the  tube  by  gravity,  or 
as  shown  in  the  illustration,  the  tube  may  be  inclined  at  a  less  angle  and  a 
jarring  or  shaking  mechanism  be  provided  for  causing  the  material  to  flow 
properly.  As  shown,  the  carrying  frame  for  the  tube  is  movably  supported  by  a 
hinge  at  its  lower  end  and  rests  at  its  upper  end  upon  a  rotating  cam. 


FIG.  47c. 

To  suppress  the  tendency  of  catalytic  materials  to  heat  or  take 
fire  on  exposure  to  oxygen,  air  or  other  gases  containing  oxygen, 
Morey  *  exposes  the  catalytic  material  to  a  partial  vacuum  for  a 
sufficient  length  of  time  to  practically  remove  the  occluded  gas  which 
is  absorbed  by  or  associated  with  the  particles  of  catalytic  material. 

Exposure  to  a  partial  vacuum,  as  complete  as  circumstances  will  permit  and 
maintained  for  a  sufficient  length  of  time,  renders  the  catalytic  substance  prac- 
tically free  from  occluded  gas  and  capable  of  being  exposed  to  air  without 
developing  undesirable  pyrophoric  action.  This  method  can  be  applied  to  the 
various  catalytic  metals,  such  as  finely-divided  nickel,  cobalt  or  platinum.  The 
catalytic  material  is  placed  in  an  air-tight  vessel  which  is  connected  with  a  vac- 
uum pump.  The  latter  can  be  operated  continuously  or  intermittently.  The 
vacuum  vessel  may  be  heated.  A  satisfactory  practice  is  to  operate  the  pump 
until  the  partial  vacuum  in  the  vessel  has  attained  the  limit  which  the  pump 
can  produce.  The  vessel  is  then  sealed  by  closing  a  stop  cock  in  the  passage 

*  U.  S.  Patent  No.  1,127,911,  February  9,  1915. 


THE  BASE  METALS  AS  CATALYZERS  159 

leading  to  the  pump.  The  catalyzer  is  allowed  to  remain  under  this  reduced 
pressure  for  about  twelve  hours,  during  which  time  the  occluded  gas  gradually 
leaves  the  catalyzer  and  the  latter  becomes  practically  non-pyrophoric.  If 
desired,  however,  the  period  of  rest  may  be  shortened  to  about  three  hours  and 
the  pump  be  operated  o,gain  to  remove  as  far  as  practicable  the  gas  which  has 
become  liberated  during  the  period  of  rest,  and  this  second  operation  of  the  pump 
may  be  followed  by  another  period  of  rest.  An  inert  gas,  for  instance,  nitrogen, 
may  be  admitted  to  the  vacuum  vessel  at  the  end  of  the  period  of  rest  and 
the  vessel  again  exhausted.  The  gas  so  admitted  to  the  vacuum  vessel  mingles 
with  the  liberated  gas  in  the  vessel  and  is  said  to  facilitate  the  removal  of  the 
rest  of  the  occluded  or  liberated  gas.  The  desired  non-pyrophoric  condition 
has  been  produced  when  a  sample  of  the  material  under  treatment  does  not  heat 
when  exposed  to  the  atmosphere. 

A  nickel  catalyst  for  use  in  hydrogenating  oils  is  prepared  by 
Morey  and  Craine  *  in  the  following  manner: 

An  insoluble  nickel  compound  such  as  the  hydroxide,  and  fuller's  earth,  are 
suspended  together  in  water  (after  heating  the  fuller's  earth  sufficiently  to  drive 
off  moisture  and  gases  from  it)  and  the  intimately  associated  mixture  of  nickel 
hydroxide  and  fuller's  earth  thus  obtained  is  dried,  comminuted  and  reduced 
with  hydrogen  to  form  a  catalyst  suitable  for  hydrogenating  oils  or  fats.  For 
example,  60  parts  of  nickel  sulphate  may  be  used  to  prepare  the  hydroxide  which 
is  mixed  with  25  parts  of  fuller's  earth. 

A  process  of  making  a  nickel  catalyst  is  described  by  Burchenal,t 
according  to  which,  sulphate  of  nickel  is  dissolved  in  water  and 
sodium  carbonate  added  to  precipitate  nickel  carbonate,  which  is 
washed,  dried  and  calcined  to  eliminate  carbon  dioxide  and  thereby 
form  an  oxide.  This  product  is  reduced  to  finely-divided  nickel  by 
heating  in  a  current  of  hydrogen.  To  render  the  product  non-pyro- 
phoric, it  may  be  cooled  in  an  atmosphere  of  hydrogen  or  carbon 
dioxide.  The  nickel  is  used  without  a  carrier  in  the  hydrogenation 
of  unsaturated  fatty  acids  or  their  esters. 

The  protection  of  a  pyrophoric  catalyst  by  incorporation  with 
fatty  material  is  described  by  Oswald  and  Doering,|  who  consider 
hardened  oil  a  desirable  protective  agent. 

The  product  is  prepared  simply  by  mixing  any  suitable  catalyst  of  a  pyrophoric 
nature,  wthout  access  of  air,  with  the  fatty  material  in  a  melted  condition,  if 
the  latter  s  solid  at  ordinary  temperature,  then  permitting  the  whole,  while 
being  agitated,  to  cool  to  a  point  just  above  its  melting-point,  when  the  whole 
mass  is  poured  into  any  convenient  receptacle  for  use,  storage  or  shipment. 
Or  the  finely-distributed  freshly-reduced  unused  metal  is  introduced  into  a  vessel 
containing  such  fat  in  a  liquid  state  and  under  an  atmosphere  of  hydrogen  and 
the  whole  permitted,  while  being  agitated,  to  cool.  The  fat  with  which  the 

*U.  S.  Patent  No.  1,232,830,  July  10,  1917;    J.  S.  C.  I.,  1917,  1039. 
tU.  S.  Patent  No.  1,226,945,  May  22,  1917. 
tU.  S.  Patent  No.  1,187,775,  June  20,  1916. 


160  THE  HYDROGENATION  OF  OILS 

finely-distributed  active  metal  is  incorporated  acts  as  a  protective  and  shielding 
agent.  The  quantity  of  fat  used  may  vary  within  considerable  Hmits,  equal 
parts  of  the  agent  and  fat  making  a  satisfactory  article.  With  about  equal 
amounts  of  readily  solidifying  fat  and  catalytic  agent,  this  result  is  obtained 
and  an  article  of  desirable  consistency,  readily  handled,  and  subdivided  is  ob- 
tained. It  carries  a  substantial  amount  of  catalyst;  an  amount  sufficient  for 
the  treatment  of  many  times  the  amount  of  oil  or  fat  it  contains.  On  placing 
it  in  hot  oil,  the  fat  melts  and  dissolves;  and  if  it  be  of  the  same  nature  as  the 
fat  to  be  produced  from  such  oil,  its  presence  does  not  change  in  any  way  the 
nature  of  the  final  product.  In  any  event,  the  amount  which  is  used  with  the 
agent  is,  relative  to  the  amount  of  oil  which  can  be  treated  with  a  given  amount 
of  agent,  wholly  insignificant. 

Colloidal  nickel  or  other  colloidal  metal  catalyzer  may  be  advan- 
tageously sealed  in  hydrogenated  oil.* 

The  handling  and  shipment  of  catalytic  material  in  a  special 
manner  is  described  by  Sulzberger.f 

A  catalyst,  for  instance,  such  as  is  obtained  by  rendering  nickel  silicate 
catalytically  active  by  subjecting  to  reduction  by  means  of  hydrogen,  after  such 
reduction  is  immediately  cooled  while  still  in  the  atmosphere  of  the  hydrogen, 
and  covered  with  hydrogenated  cottonseed  oil,  which  will  solidify  to  a  solid  mass. 
In  this  condition  the  catalyst  can  be  kept  as  well  as  shipped  to  points  for  its  use. 
The  homogeneous  nature  of  the  product  makes  it  possible  to  procure  desired 
quantities  of  the  nickel-catalyst  by  simply  weighing  off  amounts  of  the  mass  or 
taking  pieces  of  certain  size  and  bulk.  The  mass  may  contain  lines  or  markings, 
from  which  the  amounts  of  catalyst  contained  in  pieces  of  certain  size  may  be 
judged,  so  as  to  make  weighing  off  of  desired  quantities  unnecessary.  The  mass 
may  also  be  formed  in  individual  pieces  (cubes,  tablets,  balls,  etc.)  containing 
definite  amounts  of  the  catalytic  agent. 

CATALYZER  POISONS 

Sabatier  and  Espil  {  have  concluded  that  the  effect  of  sulphur 
and  the  halogens  as  catalyzer  poisons  has  been  exaggerated. 

Traces  of  these  substances  do  not  appear  sufficient  to  destroy  the  activity 
of  nickel.  For  example  benzene  containing  0.5  per  cent  iodine  in  solution  was 
completely  transformed  into  cyclohexane.  The  nickel  in  about  one-half  of  the 
hydrogenating  tube  toward  the  inlet  side  was  affected  but  the  catalyzer  in  the 
other  half  of  the  tube  remained  active.  Chlorine  and  bromine,  introduced 
as  hydrochloric  or  hydrobromic  acids  or  as  halogenated  benzol,  also  sulphur  in 
the  form  of  carbon  bisulphide,  acted  in  a  similar  manner.  Moreover  the  nickel 
which  is  rendered  inactive  to  benzol  still  preserves  the  power  of  carrying  hydrogen 
to  nitrils  and  other  aliphatic  or  aromatic  organic  compounds  but  is  incapable  of 
hydrogenating  ketones  or.  ethylene  hydrocarbons.  Sabatier  and  Espil  recom- 
mend that  nickel  poisoned  by  chlorine  be  revivified  by  using  it  to  hydrogenate 

*  Ellis,  U.  S.  Patent  1,226,620,  May  15,  1917;  Reissue  14,429,  Jan.  29,  1918. 
t  U.  S.  Patent  No.  1,223,123,  April  17,  1917. 
JBull.  Soc.  Chim.,  Vol.  XV.,  1914,  778. 


THE  BASE  METALS  AS  CATALYZERS  161 

nitrobenzene.  After  a  few  hours  use  in  this  manner  the  catalyzer  is  reactivated 
and  will  convert  benzene  into  cyclohexane.  When  poisoned  by  bromine  or  iodine 
this  treatment  is  not  effective. 

Potassium  cyanide  was  found  by  Peters  *  to  poison  palladium 
catalyzer. 

A  method  of  removing  catalyzer  poisons  from  oil,  recommended 
by  the  author  f  is  to  treat  the  oil  with  catalyzer  which  has  lost  its 
catalytic  activity. 

To  this  end  a  finely-divided  spent  nickel  catalyzer  is  vigorously  agitated  with 
the  oil  at  a  temperature  of  about  180°  C.  until  catalyzer  poisons  have  been 
absorbed  when  the  oil  is  filtered,  fresh  catalyzer  added  and  hydrogenation  is 
completed.  The  treatment  of  the  oil  depends  upon  the  character  of  the  catalyzer 
poisons  present.  Aluminum,  nickel,  copper,  etc.,  and  their  basic  compounds  in  a 
finely-divided  state  can  be  used. 

One  of  the  main  difficulties  in  the  hydrogenation,  by  the  aid  of 
nickel  catalyzer,  of  many  low-grade  oils,  such  as  some  of  the  fish 
and  whale  oils,  is  that  the  life  of  the  catalyzer  is  relatively  very 
short.  Ellis  and  Wells  {  have  studied  the  problem  of  treating  such 
oils  to  adapt  them  to  the  hydrogenation  process. 

Usually  the  activity  of  the  catalyzer  becomes  much  slower  after  two  or  three 
batches  of  oil  have  been  hardened  and  in  some  cases  it  is  necessary  to  prepare 
fresh  catalyzer  for  every  batch  of  oil  treated.  On  the  other  hand,  when  harden- 
ing a  good  grade  of  oil,  such  as  refined,  edible  cottonseed  oil,  the  life  of  a  care- 
fully prepared  catalyzer  is  likely  to  be  very  long  and  in  some  cases  an  entirely 
new  lot  of  catalyzer  is  not  required  for  months  in  the  constant  operation  of  a 
hardening  plant.  In  these  cases  the  catalyzer  is  kept  in  a  state  of  high  activity 
for  continued  usage  by  adding  a  small  amount  of  fresh  catalyzer  at  intervals  of 
one  or  two  weeks.  It  has  been  observed  that  some  kinds  or  grades  of  oil  may 
be  hydrogenated  to  an  incomplete  degree  but  that  they  cannot  be  carried  beyond 
this  point,  no  matter  how  long  the  treatment  is  continued,  without  change  of 
catalyzer.  If  to  these  semi-hardened  oils  a  fresh  quantity  of  catalyzer  is  added 
the  hardening  will  usually  proceed  practically  to  complete  saturation.  In  some 
cases,  a  fresh  quantity  of  oil  may  be  treated  with  the  seemingly  spent  catalyzer, 
when  partial  hardening  will  occur.  An  additional  quantity  of  fresh  catalyzer 
will  sometimes  carry  the  oil  so  treated,  to  completion,  showing  that  the  sub- 
stance which  affects  the  catalyzer  is  apparently  taken  up  by  it  under  these  cir- 
cumstances, thus  leaving  the  oil  in  condition  to  be  readily  hardened.  Some  oils 
which  ordinarily  cannot  be  hardened  without  a  preliminary  purifying  treatment, 
may  first  be  agitated  with  a  spent  catalyzer,  the  catalyzer  removed  and  the 
oil  then  incorporated  with  a  fresh  quantity  of  catalyzer  when  hardening  readily 
occurs. 

*  Inaugural  Dissertation,  Leipsic,  1913. 
tU.  S.  Patent  No.  1,132,710,  March  23,  1915. 

JJ.  Ind.  Eng.  Chem.,  1916,  886.  See  also  U.  S.  Patent  to  Ellis,  1,247,516,  Nov.  20, 
1917. 


162  THE  HYDROGENATION  OF  OILS 

Cod  Oil.  Crude  cod  oil  was  freed  from  fatty  acids  with  a  solution  of  sodium 
carbonate  and  after  washing  free  from  alkali  and  soap  was  treated  with  hydro- 
gen, using  5  per  cent  catalyzer  prepared  from  nickel  oxide.  In  several  trials, 
the  oil  either  did  not  harden  at  all,  or  only  to  a  very  minor  degree.  Other 
forms  of  catalyzer  were  equally  ineffective.  The  oil  was  then  agitated  for  one 
hour  at  200°  C.  with  freshly-prepared  copper  hydrate,  filtered  to  remove  the 
copper  compound  and  again  treated  with  hydrogen  and  catalyzer  under  the  same 
conditions  as  above.  The  oil  was  readily  hardened  by  this  treatment.  Another 
sample  of  the  oil,  refined  as  above,  was  treated  with  5  per  cent  freshly-prepared 
silver  oxide  at  200°  C.  for  one  hour.  The  silver  compound  was  removed  by 
filtration  and  the  clear  oil  hydrogenated.  In  a  short  time  this  oil  was  hardened 
to  a  melting-point  of  46°  C.  on  hydrogenating  under  the  same  conditions  as 
above. 

A  series  of  tests  were  performed  to  determine  the  relative  value  of  freshly- 
precipitated  copper  hydrate  as  a  detoxicating  agent.  In  one  test,  portions  of 
cod  oil  were  agitated  with  5  per  cent  of  freshly-prepared  copper  hydrate,  com- 
mercial copper  carbonate  and  lead  oxide  at  180°  to  200°  C.  for  two  hours.  After 
filtering,  these  samples  were  treated  with  hydrogen  using  5  per  cent  nickel  oxide  as  a 
source  of  catalyzer.  This  was  reduced  in  oil  at  250°  C.  for  one-half  hour.  The 
hydrogenation  operation  was  carried  out  at  230°  C.  for  three  hours.  The  oil 
treated  with  freshly-precipitated  copper  hydrate  hardened  to  a  melting-point  of 
53°  to  54°  C.,  the  oil  treated  with  copper  carbonate  hardened  slightly,  while  the 
oil  treated  with  lead  oxide  did  not  harden. 

To  determine  the  most  effective  temperature  for  treating  the  oil  with  copper 
hydrate  the  following  tests  were  performed:  Cod  oil  was  agitated  with  \  per 
cent  of  copper  hydrate  for  one  hour  at  room  temperature,  then  was  filtered  and 
subjected  to  the  hydrogenation  process.  Another  portion  of  the  oil  was  treated 
in  a  similar  manner,  except  the  temperature  of  treatment  with  copper  hydrate 
was  50°  C.  Other  portions  were  treated  at  75°  and  at  110°  to  120°  C.  The 
samples  treated  below  110°  C.  did  not  harden  and  metallic  mirrors  were  formed 
on  the  walls  of  the  container  during  the  treatment  with  hydrogen.  The  sample 
which  was  agitated  at  room  temperature  exhibited  the  most  perfect  mirror.  The 
oil  treated  at  110°  to  120°  C.  hardened  readily  without  the  formation  of  a  mirror. 

The  effect  of  refining  cod  oil  with  alkali  before  hydrogenation,  when  the 
copper  hydrate  treatment  is  used,  is  beneficial  to  the  catalyzer  as  was  shown  by 
agitating  crude  cod  oil  with  copper  hydrate  at  140°  to  150°  C.  for  one  hour, 
filtering  and  then  subjecting  it  to  the  hydrogenation  process,  using  nickel  oxide. 
The  catalyzer  was  formed  in  the  oil  at  250°  C.  and  hydrogenation  was  carried 
out  at  190°  to  200°  C.  for  four  hours.  The  oil  was  only  slightly  hardened. 

A  quantity  of  the  oil  under  examination  was  burned  in  oxygen  in  a  combustion 
bomb.  The  contents  of  the  bomb  were  washed  out  and  examined  qualitatively. 
Sulphates  and  a  trace  of  iodine  compounds  were  found  to  be  present  but  no  test 
was  obtained  for  either  chlorides  or  phosphates.  Either  sulphur  in  the  sulphide 
form,  or  iodine  could  have  been  responsible  for  the  poisoning  action  on  the  cat- 
alyzer noted. 

Manhaden  Oil.  Southern  crude  fish  (menhaden)  oil,  without  refining,  was  sub- 
jected to  the  hydrogenation  process,  using  nickel  oxide  reduced  in  the  oil  at 
250°  C.  and  the  hydrogen  treatment  was  carried  out  at  200°  C.  for  four  hours. 
The  oil  was  not  hardened.  Another  portion  of  the  same  oil  was  agitated  with 
copper  hydrate  at  135°  to  150°  C.  for  one  hour  and  treated  under  the  same  con- 


THE  BASE  METALS  AS  CATALYZERS  163 

ditions  as  above.  The  oil  was  hardened,  without  difficulty,  to  a  melting-point 
of  45°  to  46°  C.  Another  quantity  of  the  same  crude  fish  oil  was  refined  and 
then  treated  with  copper  hydrate.  The  treated  oil  was  hydrogenated  using  a 
catalyzer  which  had  previously  been  used  in  cod  oil  that  had  been  detoxicated 
with  copper  hydrate.  The  oil  hardened  to  a  melting-point  of  52°  to  53°  C. 
The  catalyzer  was '  apparently  not  affected  by  its  previous  use  in  cod  oil  which 
had  been  treated  with  copper  hydrate. 

Herring  oil  which  could  not  be  hardened  by  the  usual  methods  was  refined 
to  free  it  from  fatty  acids  and  after  treating  with  copper  hydrate  for  one  hour 
at  110°  to  120°  C.  was  subjected  to  the  action  of  hydrogen  in  the  presence  of  a 
catalyzer  prepared  by  reducing  nickel  oxide  in  the  oil  at  250°  C.  for  one-half 
hour.  The  oil  was  hydrogenated  at  190°  to  200°  C.  for  five  hours.  It  hardened 
to  a  melting-point  of  45°  to  46°  C. 

Dogfish  Oil.  This  oil  has  proved  somewhat  difficult  to  hydrogenate.  Jn  one 
case,  a  sample  of  the  oil  was  agitated  with  copper  hydrate  for  one  hour  and  then 
treated  with  hydrogen,  using  a  catalyzer  prepared  by  precipitating  nickel  hydrate 
on  a  carrier  and  reducing  at  360°  C.  Hydrogenation  was  conducted  for  5£  hours 
at  180°  to  190°  C.  The  oil  did  not  harden.  The  catalyzer  was  filtered  out  and 
5  per  cent  of  a  mixture  of  finely-divided  nickel-copper  hydrate  was  added.  A 
current  of  hydrogen  was  passed  through  the  oil,  the  temperature  of  the  oil  being 
held  at  250°  C.  for  one-half  hour,  then  lowered  to  190°  to  200°  C.  and  main- 
tained at  that  point  for  three  hours.  The  oil  hardened  to  a  melting-point  of 
45°  C. 

It  has  generally  been  assumed  that  the  presence  of  sulphates  in  a 
nickel  catalyzer  is  prejudicial  but  repeated  tests  by  the  author  have 
shown  this  not  to  be  the  case  under  certain  conditions.  If  the  sulphate 
is  of  a  difficultly  reducible  character  as,  for  example,  sodium  sulphate, 
the  nickel  is  practically  unaffected,  especially  if  the  reduction  has 
taken  place  at  a  relatively  low  temperature.  When  a  mixture  of  nickel 
hydrate  or  carbonate  and  sodium  sulphate  is  reduced  at  a  temperature 
somewhat  below  250°  C.  the  activity  of  the  catalytic  nickel  is  not 
materially  affected  by  the  sulphate.  Apparently  sulphur  in  the  sul- 
phide form  is  necessary  in  order  to  poison  the  catalyzer.  Catalytic 
material  containing  sulphates  has  been  employed  on  a  commercial 
scale  in  this  country  for  a  considerable  period  of  time  with  satisfactory 
results. 

The  effect  of  sulphur  and  arsenic  in  hydrogen  gas  employed  for  oil  hardening  has 
been  investigated  by  Hehner  and  reported  by  Crossley.*  Curves  of  absorption 
were  obtained  which  indicate  the  deleterious  action  of  arsenic  and  sulphur.  Un- 
purified  hydrogen  such  as  was  obtained  from  a  good  specimen  of  zinc  and  acid 
did  not  permit  the  catalyzer  to  function  as  actively  as  in  the  case  of  pure  hydrogen. 
When  hydrogen  was  passed  through  a  very  dilute  solution  of  hydrogen  sulphide  in 
water  the  effect  on  the  catalyzer  was  very  marked.  The  effect  of  using  crude  water 
gas  containing  about  28  per  cent  of  hydrogen  in  comparison  with  water  gas  which 

*  Pharm.  Soc.  April  21,  1914;  Pharm.  J.  1914,  92,  604,  637  and  676;  J.  S.  C.  I.,  1914, 
1135. 


164 


THE  HYDROGENATION  OF  OILS 


has  passed  through  soda  lime  is  shown  by  Hehner.     The  purified  water  gas  permitted 
catalytic  action  to  go  on  to  better  advantage. 

EFFECT  OF  HALOGENS,  HALOGEN  COMPOUNDS,  SULPHUR,  ETC., 
ON  HYDROGENATION  OF  COTTONSEED  OIL  * 

CATALYZER:  NICKEL  OXIDE  (5  PER  CENT  OF  THE  WEIGHT  OF  THE  OIL)  REDUCED 
IN  OIL  AT  250°  C.  FOR  ONE-HALF  HOUR 


Expt.  No. 

Substance  Added. 

Per  cent 
Added. 

Temp., 
°C. 

Time, 
Hours. 

Effect  on  Oil. 

1 

Bromine  

1  0 

200 

2 

No  hardening 

KCH) 
2 

Iodine 

1.0 
1  0 

200 
200 

2 
2 

2  (CH) 
3 
3(CH) 
4 
4(CH) 
5 
6 

Antimony  Bromide  .... 

Sodium  Chloride  
Zinc  chloride  

1.0 
0.5 
0.5 
1.0 
1.0 
5.0 
5  0 

200 
200 
200 
200 
200 
210 
210 

2 
2£ 
2| 
2 
2 

21 

2i 

Oil  hardened 
Oil  polymerized 

7 
7  (CH) 
8 
9 

Tin  chloride  

1.0 
1.0 
0.5 
1  0 

200 
200 
200 
200 

2| 
2| 
2^ 
2 

Slight  hardening 
Oil  hardened 

10 

Sulphur  

0  5 

200 

2± 

Slight  hardening 

10  (CH) 
11 
11  (CH) 
Blank 
12 

Sulphur 

0.5 
1.0 
1.0 

0  1 

200 
200 
200 
200 
210 

2£ 
2| 
2^ 
2| 
31 

Oil  hardened 
No  hardening 
Oil  hardened 

13 

13  (CH) 
14 
14  (CH) 
15 
15  (CH) 
16 

Red  phosphorus  

Sulphur  chloride  
(As2O3).. 

1.0 
1.0 
0.5 
0.5 
1.0 
1.0 
1  0 

200 
200 
200 
200 
200 
200 
200 

2 
2 
2 
2 
2 
2 
2 

Slight  hardening 
Oil  hardened 
Slight  hardening 
Oil  hardened 
No  hardening 
Oil  hardened 
No  hardening 

17 

Mercury 

1  0 

200 

2 

Slight  hardening 

Blank 
18 

Lead  stearate.    . 

1.0 

200 
200 

2^ 
2? 

Oil  hardened 
No  hardening 

19 

Lead  oleate. 

1  0 

200 

2| 

19  (CH) 

1.0 

200 

2^ 

(CH)  after  an  experiment  number  indicates  treatment    with    copper    hydrate 
before  hydrogenation. 

Kelber  f  has  found  that  nickel  catalyzers  made  in  different  ways 
behave    entirely    differently,  in  reducing  reactions,    toward    contact 

*  Ellis  and  Wells,  J.  Ind.  Eng.  Chem.,  1916,  886.     t  Ber.  49,  1868. 


THE  BASE  METALS  AS  CATALYZERS  165 

poisons  such   as   hydrocyanic  acid  or   potassium    cyanide,   hydrogen 
sulphide  and  carbon  bisulphide. 

The  following  catalyzers  (a)  from  basic  nickel  carbonate  reduced  at  450°  in 
hydrogen  (6)  from  basic  nickel  carbonate  reduced  in  hydrogen  at  310°  and  (c)  from 
basic  nickel  carbonate  on  inorganic  carriers  reduced  in  hydrogen  at  450°,  show  a 
sensitiveness  to  these  poisons,  decreasing  in  the  order  (a),  (6)  and  (c).  This  is  believed 
to  be  due  to  the  fact  that  the  high  temperature  at  which  (a)  is  prepared  changes  the 
surface  of  the  individual  particles  of  the  catalyzer  so  that  there  remain  only  a  few 
points  on  these  particles  which  are  capable  of  adding  hydrogen  and  acting  as  a  carrier 
of  it,  and  these  points,  being  more  reactive  than  the  rest  of  the  nickel  are  the  first  to 
act  on  the  poison,  so  that  relatively  small  amounts  of  the  latter  are  able  to  poison 
the  whole  of  the  catalyzer.  The  lower  temperature  used  in  preparing  (6)  leaves 
more  of  these  active  spots,  while  in  (c)  the  presence  of  the  inorganic  skeleton 
doubtless  hinders  the  change  in  the  surface  of  the  catalyzer.  The  experiments 
were  carried  out  at  room  temperature  under  atmospheric  pressure  in  a  shaking 
apparatus,  0.5  g.  of  the  metal  being  shaken  twenty  minutes  with  the  poison  in 
25  cc.  water  in  a  hydrogen  atmosphere,  then  treated  with  C6H5CH:CHCO2Na 
(0.75  g.  acid  and  somewhat  more  than  the  calculated  amount  of  caustic  soda  in 
25  cc.  water)  and  the  absorption  of  hydrogen  measured  every  five  minutes. 
Below  are  given  the  per  cent  of  its  original  value  to  which  the  reducing  power 
of  the  3  catalyzers  is  decreased  by  varying  amounts  of  the  different  substances 
in  the  first  fifteen  minutes.  Potassium  cyanide:  (a)  0.00005  g.,  45  per  cent; 
0.0003  g.,  2  per  cent;  (6)  0.0003  g.,  55  per  cent;  0.001  g.,  0  per  cent,  (c), 
0.002  g.,  25  per  cent;  0.02  g.,  2  per  cent.  (It  is  not  clear  in  the  original  whether 
the  amounts  given  above  represent  the  weights  of  potassium  cyanide  used  or 
the  amounts  of  hydrocyanic  acid  equivalent  to  the  salt  used.)  Hydrocyanic 
acid:  (a)  0.0005  g.,  63  per  cent;  0.002  g.,  1  per  cent.  (6),  0.001  g.,  50  per  cent; 
0.005  g.,  0  per  cent.  Traces  of  alkalies  give  entirely  different  values  and  as  (c) 
could  not  be  entirely  freed  of  alkalies  it  was  not  used  in  this  series.  The  small 
"  toxity  "  of  hydrocyanic  acid  as  compared  with  potassium  cyanide  is  ascribed 
to  the  rapid  change  of  hydrocyanic  acid  in  the  presence  of  nickel  and  hydrogen; 
the  catalyzers  poisoned  with  hydrocyanic  acid  retain  only  traces  of  the  poison, 
whereas  with  potassium  cyanide,  the  catalyzer  shows  large  amounts  of  the 
poison,  although  in  a  changed  form.  To  test  the  effect  of  hydrocyanic  acid, 
potassium  cyanide  and  nickel  cyanide  on  the  catalyzer,  (6),  after  saturation 
with  hydrogen  was  shaken  in  hydrogen  to  constancy  of  volume  with  definite 
amounts  of  solutions  of  the  3  substances,  filtered  and  the  poison  determined 
in  the  solid  and  the  filtrate;  the  filtrate  was  found  to  be  free  from  hydrocyanic 
acid  but  to  be  strongly  alkaline  and  contain  ammonia,  probably  produced  by  a 
catalytic  reduction  of  hydrocyanic  acid  or  a  nickel  cyanide  compound,  as  several 
cc.  of  hydrogen  were  always  used  up;  the  solid  nickel,  when  dissolved  in  sul- 
phuric acid  and  heated  with  alkali,  gave  a  distillate  containing  ammonia;  no 
amines,  or  only  traces  at  most,  were  found  in  the  solid  or  filtrate.  A  catalyzer 
poisoned  with  potassium  cyanide,  then  filtered  and  washed  with  water,  does  not 
recover  its  activity,  but  this  can  be  restored  by  treating  once  with  hydrogen  and 
warming  with  ammonia,  or,  best,  by  boiling  with  caustic  soda. 

Hydrogen  sulphide:  (a)  0.001  g.,  25  per  cent;  0.005  g.,  1  per  cent.  (6)  0.01 
g.,  15  per  cent;  0.02  g.,  0  per  cent,  (c)  0.02  g.,  60  per  cent;  0.1  g.,  0  per  cent. 
The  sulphur  is  found  almost  entirely  as  sulphide,  in  the  solid  nickel. 


166  THE  HYDROGENATION  OF  OILS 

- 

Carbon  bisulphide:  (a)  0.0005  g.,  25  per  cent;  0.003  g.,  0  per  cent.  (6) 
(6)  0.003  g.,  60  per  cent;  0.01  g.,  1  per  cent,  (c)  0.01  g.,  63  per  cent;  0.06  g., 
3  per  cent.  Practically  all  of  the  sulphur  found  (corresponding  to  about  50  per 
cent  of  that  in  the  carbon  bisulphide  used)  was  in  the  solid  nickel  as  sulphide, 
with  only  traces  in  the  filtrate. 

The  effect  of  catalyzer  poisons  has  also  been  studied  by  Moore, 
Richter  and  Van  Arsdel.*  The  experiments  on  poisons  were  carried 
out  in  an  apparatus  containing  oil  and  catalyzer,  through  which 
hydrogen  was  bubbled.  A  mixture  of  oil  with  1  per  cent  nickel  on  a 
carrier  was  hydrogenated  first  for  one  hour  to  ascertain  the  original 
activity  of  the  catalyzer.  At  the  end  of  the  hour,  2  per  cent  of 
the  finely  powdered  solid  substance  in  question  was  added,  and  the 
hydrogenation  continued.  Samples  were  then  taken  at  intervals  to 
determine  the  further  fall  of  the  iodine  number,  and  the  poisoning 
effect  was  judged  by  the  shape  of  the  iodine  number-time  curve, 
compared  to  one  in  which  no  poison  was  present.  The  results  may 
be  summarized  as  follows: 

Substance.  Effect  on  Activity. 

Sulphur Destroyed  immediately 

Na2S-9H2O Gradually  destroyed 

NaCl No  effect 

Na2SO4 No  effect 

NaNO3 No  effect 

NiCl2-6H2O No  effect 

Reduced  iron No  effect 

The  three  gases  £[28,  862  and  Cl2  were  also  tried.  In  each  case 
the  activity  was  destroyed  immediately.  A  small  amount  of  water 
vapor  in  the  hydrogen  was  found  gradually  to  destroy  the  activity 
of  the  catalyzer. 

Concerning  the  phenomena  of  catalytic  poisons,  Bancroft  f  remarks 
that  the  adsorption  of  reacting  substances  and  consequently  reaction 
velocity  are  decreased  by  the  presence  on  the  solid  catalytic  agent,  of  a 
film  of  solid,  liquid,  or  gas.  Very  small  amounts  of  grease  will  keep 
palladium  from  taking  up  hydrogen.  Carbon  monoxide  may  act  as 
a  catalytic  poison  by  decreasing  the  adsorption  of  other  substances. 
It  is  very  tenaciously  held  by  platinum.  Reaction  products  may 
decrease  reaction  velocity  by  hindering  diffusion  of  reacting  substances 
to  the  catalytic  agent  and  by  decreasing  their  adsorption. 

The  work  of  Maxted  J  indicates  carbon  monoxide  to  retard  the 

*J.  Ind.  Eng.  Chem.,  1917,  451. 

f  J.  Phys.  Chem.,  1917,  21,  734;   Chem.  Abs.,  1918,  12,  328. 

J  Trans.  Faraday  Soc.,  1917  (advance  copy) ;    Chem.  Trade  J.  61.  509-10. 


THE  BASE  METALS  AS  CATALYZERS  167 

rate  of  addition  of  hydrogen  to  fatty  oils.  The  inhibitive  effect  of 
carbon  monoxide  was  studied  from  a  quantitative  standpoint  for  the 
hydrogenation  of  olive  oil  using  finely-divided  nickel  as  catalyst. 
The  experiments  were  carried  out  with  10  g.  of  oil  and  0.1  g.  of 
nickel,  using  pure  hydrogen,  and  hydrogen  containing  0.25,  0.5,  1.0 
and  2  per  cent  of  carbon  monoxide  respectively.  The  absorption 
was  noted  at  five-minute  intervals  for  one  hour,  at  the  end  of  which 
pure  hydrogen  showed  584.5  cc.  absorption,  hydrogen  containing 
0.25  per  cent  carbon  monoxide,  393.9  cc.;  hydrogen  containing  0.5 
per  cent,  309.6  cc. ;  hydrogen  containing  1.0  per  cent,  235.2  cc.; 
and  hydrogen  containing  2  per  cent,  158.8  cc.  Maxted  considers 
these  results  to  show  a  marked  poisoning  influence  by  carbon  monox- 
ide, an  effect  which  was  differentiated  from  the  calculated  obstruc- 
tive effects  of  the  impurity.  The  first  traces  of  carbon  monoxide 
have  relatively  the  greatest  retarding  influence  on  the  velocity  of 
hydrogenation. 

Pierron  *  gives  a  lengthy  description  of  an  ignition  catalyst  having  the  following 
properties.  "  A  porous  or  finely-divided  matter  or  product  (or  mixture  of 
products)  constituting  in  some  manner  a  support  serving  to  prevent  agglomeration 
of  the  second  product.  This  matter  or  product  or  mixture  of  matters  or  products 
is  termed  the  supporting  element."  The  catalytic  agent  employed  is  platinum, 
palladium  or  similar  rare  metal,  supported  on  an  oxide  of  silicon,  aluminum,  iron, 
manganese,  etc. 

Hagemann  and  Baskerville  carry  out  hydrogenation  by  means  of  a 
catalyzer  of  nickel  sheet,  wire  or  other  nickel  "  shapes  "  having  a 
coherent  layer  of  nickel  oxide  closely  adhering  to  the  metal  surf  ace.  f 
In  using  these  "  oxide-tarnished  "  metal  shapes,  hardened  fats  are 
said  to  be  obtained  in  a  remarkably  clean  undiscolored  state. 

Elworthy  J  states  that  copper  or  other  metals  as  wire  or  sheets  coated 
with  nickel  may  be  used  as  catalytic  material. 

An  organosol  adapted  for  use  as  a  catalyst  in  fat  hardening  is 
prepared  by  Karplus  §  as  follows: 

An  irreversible  colloid  is  removed  from  a  hydrosol  by  producing  within  the 
latter  an  amorphous  organic  precipitate  which  is  soluble  in  the  organic  substance 
in  which  it  is  desired  to  produce  the  organosol.  The  precipitate  is  separated, 
heated  to  remove  water,  and  then  mixed  with  the  organic  substance,  when  an 
organosol  of  the  desired  colloid  is  obtained. 

*  British  Patent  No.   15,414  of  1898. 
t  U.  S.  Patent  No.  1,238,137,  August  28,  1917. 
J  U.  S.  Patent  No.  943,627,  Dec.  14,  1909. 

§J.  S.  C.  I.,  1916,  823;  British  Patent  No.  8,641,  June  11,  1915;  German  Patent 
No.  293,848,  November  13,  1913. 


168  THE  HYDROGENATION  OF  OILS 

The  addition  of  substances,  refractory  at  the  required  temperature  and  chem- 
ically inactive  towards  the  mixture,  to  increase  the  efficiency  and  the  period  of 
activity  of  contact  masses  and  to  avoid  the  possibility  of  a  reaction  between  the 
catalyst  and  the  constituents  of  the  support  of  the  contact  material  is  detailed 
by  Nitrogen  Ges.  m.b.H.*  For  example,  in  the  use  of  a  mixture  of  copper  and 
copper  oxide  as  the  catalyst,  and  clay  or  other  materials  containing  silicates  as 
the  support,  the  addition  of  aluminum  oxide  causes  the  mass  to  retain  its  activity 
for  a  longer  period.  The  reaction  between  the  copper  oxide  and  the  silicates  is 
prevented  and  the  catalyst  is  so  finely  distributed  throughout  the  mixture  that 
the  agglomeration  or  fusion  of  copper  cannot  take  place.  The  mass  is  stated  to 
possess  a  high  degree  of  porosity. 

For  the  reduction  of  oils  with  hydrogen  under  a  pressure  of  nine 
atmospheres,  an  apparatus  was  constructed  by  Hamburger,  f  resem- 
bling the  one  described  by  Stuckert  and  Enderli.J  The  influence 
of  temperature,  pressure,  divisibility  of  the  catalyst,  and  kind  of  oil 
(impurities  therein)  on  the  hydrogenation  process  was  investigated. 
The  hydrogenation  of  all  pure  oils  with  finely-divided  nickel,  as  a 
catalyst,  proceeds  without  difficulty;  the  same  holds  true  for  fatty 
acids  obtained  from  very  impure  oils  by  distillation,  with  steam 
vacuo.  The  nickel  catalyst  was  obtained  by  the  reduction  at 
260°  to  300°  of  nickel  oxide,  which  had  been  previously  precipitated 
on  pumice  stone.  It  appears,  according  to  Hamburger,  that  tung- 
sten, molybdenum,  thorium,  uranium,  zirconium,  titanium,  vanadium 
and  manganese  cannot  be  used  as  catalysts  in  the  hydrogenation  of 
oils.  He  states  that  the  claims  by  the  author  §  could  not  be  con- 
firmed, not  even  when  a  hydrogen  pressure  of  200  atmospheres  was 
applied.  1 1 

Aromatic  amines  are  obtained  by  a  process  of  the  Badische  Co.^f  by  reduction 
of  nitro  compounds,  with  hydrogen,  water  gas,  etc.,  in  contact  with  a  catalyst 
consisting  of  copper  made  by  reducing  at  a  temperature  below  red  heat  copper 
oxide  prepared  otherwise  than  pyrogenetically,  together  with  a  promoting  agent; 
precipitation  of  copper  salts  by  means  of  caustic  soda  is  a  suitable  method  of 
forming  the  oxide.  According  to  examples,  a  paste  of  coarse  pumice,  copper 
oxide,  zinc  carbonate  and  water  is  reduced  by  water  gas,  and  then  a  mixture  of 

*  French  Patent  No.  453,099,  January  13,  1913;    J.  S.  C.  I.,  1913,  741. 

fChem.  Weekblad,   13,  2-13,  1916;    Chem.  Abs.,  1916,  826. 

J  A  bomb  provided  with  a  stirrcr  for  the  intimate  mixing  of  a  liquid  and  gas  under 
high  pressure  and  temperature,  designed  to  keep  the  liquid  saturated  with  the  gas 
as  the  reaction  proceeds.  A  form  of  valve  for  reducing  pressures  is  also  described. 
(Z.  Electrochem.,  19,  570.) 

§U.  S.  Patent  No.  1,026,156. 

|j  The  observations  of  Hamburger  are  not  in  agreement  with  the  results  of  other 
investigators.  A  number  of  the  bodies  described  by  Hamburger  as  having  no  cata- 
lytic properties  have  been  found  to  serve  as  activators  or  co-catalysts  in  conjunction 
with  nickel  and  the  like. 

1  British  Patent  No.  5,692,  April  15,  1915. 


THE  BASE  METALS  AS  CATALYZERS  169 

a  nitro  compound  and  water  gas  is  passed  over  the  reduced  mass;  a  paste  of 
pumice  in  lumps,  copper  hydrate,  silver  oxide,  water-glass  and  water  is  pre- 
pared and  is  reduced  by  hydrogen  and  then  a  mixture  of  vapor  of  nitro  com- 
pound and  hydrogen  is  passed  over  the  reduced  mass;  a  solution  of  copper, 
silver  and  magnesium  nitrates  is  precipitated  with  caustic  soda,  the  washed 
precipitate  is  made  into  a  paste  with  pumice  in  lumps,  water-glass  and  water 
and  is  then  reduced  by  hydrogen.  A  mixture  of  a  nitro  compound  and  hydro- 
gen is  passed  over  the  reduced  mass. 

Walter  (Soc.  L'Oxylithe)  *  facilitates  separation  of  the  catalytic 
agent  after  the  hydrogenation  by  employing  catalysts  which  are 
either  magnetic  in  themselves,  or  may  be  rendered  temporarily 
magnetic  after  the  reaction,  or  rest  upon  magnetic  supports,  and, 
therefore  may  be  retained  within  the  vessel  by  subjecting  this  to 
the  action  of  a  magnetic  field  when  the  hydrogented  product  is 
withdrawn.  Various  devices  for  carrying  out  the  process  are  de- 
scribed. 

Reynolds  f  notes  that  the  danger  of  explosion  when  using  hydro- 
gen to  reduce  catalytic  raw  material  is  a  serious  menace  because 
the  reduction  of  the  material  being  treated  is  usually  effected  in  a 
drum  or  cylinder  that  is  heated  by  a  flame  and  the  slightest  defect 
in  the  drum  would  permit  the  escape  of  hydrogen  into  the  flame 
with  disastrous  results. 

Instead  of  hydrogen,  Reynolds  finds  ammonia  may  be  used,  or  even  carbon 
monoxide  if  rendered  non-inflammable  by  admixture  with  an  inert  gas.  Also  it 
is  possible  to  mix  hydrogen  with  inert  gas  so  that  it  is  rendered  non-explosive. 
This  inert  gas  may  be  either  carbon  dioxide  or  nitrogen  or  a  mixture  of  both, 
their  proportions  being  immaterial  so  long  as  the  percentage  of  reducing  gas  does 
not  reach  the  explosive  point.  Reynolds  states  that  even  5  per  cent  is  non- 
explosive.  He  thinks  that  the  inert  gas  appears  to  envelop  the  reducing  gas  in 
the  mixture  so  that  it  is  rendered  non-explosive  but  does  not  combine  with  it 
to  change  its  reducing  quality  in  any  degree.  While  ammonia  may  be  used 
alone,  it  may  be  also  mixed  with  the  inert  gas.  The  preferred  mixture  is  nitro- 
gen, carbon  dioxide  and  carbon  monoxide  and  a  method  of  making  it  is  to  draw 
air  through  burning  coke  in  a  closed  container;  washing  the  resulting  product 
and  then  conducting  it  into  the  reducing  drum.  The  air  after  passing  over  the 
coke  becomes  a  mixture  of  gases  containing  approximately  78  per  cent  nitrogen, 
20  per  cent  carbon  dioxide,  and  a  2  per  cent  carbon  monoxide.  This  mixture  is 
stated  to  be  efficient  as  a  reducing  agent,  is  cheap  to  make  and  is  non-explosive. 
The  resulting  catalyzer  may  be  exposed  to  the  atmosphere  for  about  thirty 
minutes  without  detriment  to  its  catalytic  properties. 

To  prepare  an  unsintered  nickel  powder  by  dry  reduction,  Ellis  t 
prepares  a  reducible  nickel  salt  or  basic  compound  such  as  the  car- 

*  French  Patent  No.  471,108,  April  18,  1914;  J.  S.  C.  I.,  1915,  162;  Seifen.  Ztg.f 
1915,  309. 

t  U.  S.  Patent  1,210,367,  December  26,  1916. 
JU.  S.  Patent  No.   1,185,075,  May  30,   1916. 


170  THE  HYDROGENATION  OF  OILS 

bonate,   hydrate  or  oxide  in  a  finely-divided  condition  as  by  pre- 
cipitation. 

For  example,  nickel  nitrate  is  precipitated  with  ammonia  and  dr'ed  with  some 
of  the  ammonium  nitrate  formed  by  the  reaction  present  in  the  precipitate.  When 
dry  the  product  is  well  washed  and  finely-divided  nickel  hydrate  in  a  substan- 
tially uncontracted  precipitated  form  is  obtained.  This  may  then  be  reduced 
with  hydrogen  under  normal  atmospheric  pressure  at  the  temperatur-e  of  say 
200°  to  300°  C.,  until  part  of  the  oxygen  is  removed.  The  partially  reduced 
product  is  then  subjected  to  hydrogen  under  a  pressure  of  about  four  or  five 
atmospheres  while  maintaining  the  temperature  at  approximately  the  same  point. 
By  the  application  of  the  hydrogen  under  pressure,  reduction  to  a  product  con- 
sisting almost  solely  of  finely-divided  metallic  nickel  takes  place  without  running 
up  the  temperature  to  a  point  where  catalytic  sensitiveness  is  lost  by  contraction 
of  the  particles  as  a  result  of  sintering  or  fritting  due  to  excessive  temperatures. 

In  an  article  on  catalysis  by  Leimdorfer  *  it  is  stated  that  by 
reducing  a  body  to  a  fine  powder  thereby  increasing  the  surface, 
new  properties  and  new  powers  are  acquired;  as  for  example,  by 
finely  dividing  metals  the  pyrophoric  condition  is  obtained,  f 

The  separation  of  nickel  and  cobalt  from  aqueous  solutions  of  their 
salts  by  hydrogen  at  high  temperatures  and  pressures  has  been  studied 

by  Ipatiew  and  Zvjagin.J 

»• 

An  investigation  of  the  displacement  of  cobalt,  from  aqueous  solutions  of 
its  sulphate,  nitrate  and  chloride  by  hydrogen  at  high  temperatures  and  pres- 
sures, shows  that  such  similar  metals  as  nickel  and  cobalt  give  in  this  way 
substances  of  different  properties,  although  the  general  character  of  the  phe- 
nomena is  the  same  as  with  copper  and  nickel  salts.  §  Cobalt  salts  show  a 
number  of  independent  reactions,  which  depend  on  critical  temperatures  and 
pressures  and  give  rise  to  separation  of  basic  salts,  the  oxide  of  the  metal,  and 
finally,  the  metal  itself. 

The  temperature  of  decomposition  of  copper  nitrate  has  been 
determined  by  Rolla.|| 

A  mixture  of  nitrogen  dioxide  (NO2)  and  oxygen,  obtained  by  the  decompo- 
sition of  lead  nitrate,  was  led  over  a  weighed  quantity  of  copper  oxide  at  tem- 
peratures of  from  70°  to  300°  C.  At  250°  C.  and  higher  temperatures,  the 
copper  oxide  showed  no  gain  in  weight,  and  hence  the  temperature  of  complete 
decomposition  of  copper  nitrate  at  atmospheric  pressure  is  given  as  250°  C. 

The  Naamloose  Vennootschap  Ant.  Jurgens  Vereenigde  Fah- 
rieken  regenerate  metallic  catalyzers  by  burning  off  the  organic 

*Seifen.   Zeitung,   1914,   1345. 

fSee  also  Seifen.  Zeitung,  1914,  1253,  1276,  1298,  1323;    1915,  303. 

t  J.  Russ.  Phys.  Chem.  Soc.,  1912,  44,  1712-1715;    J.  S.  C.  I.,  1913,  84. 

§J.  8.  C.  L,  1911,  900. 

II  Gaz.  Chim.  Ital.,  1915,  45,  1,  444-450;    J.  S.  C.  I.,  1915,  796. 


THE  BASE  METALS  AS  CATALYZERS  171 

material,  when  the  catalyzer  can  be  used  immediately  or  after  reduc- 
tion in  a  current  of  hydrogen.* 

The  regeneration  of  nickel  catalysts  is  carried  out  by  the  Soc.  Indus- 
trielle  de  Products  Chimiques^  by  wholly  or  partially  removing  adherent 
organic  matter,  as  by  solution  and  then  heating  the  residue  while  stirring 
with  access  of  air.  The  product  may  be  washed  with  water  and  again 
heated  to  redness.  It  is  then  ready  for  use  as  oxide ;  or  the  oxide  may  be 
reduced  to  suboxide  by  heating  to  about  300°  with  about  its  own  weight 
of  oil  in  a  current  of  hydrogen.  A  catalyst  consisting  of  metallic  nickel 
may  be  obtained  by  reducing  at  a  low  temperature  the  nickel  oxide 
catalyst  described  above  or  heating  the  original  spent  catalyst  wholly 
or  practically  freed  from  organic  matter,  without  access  of  air  or  in 
presence  of  a  reducing  agent. 

For  the  preparation  of  reduced  nickel  Lanef  employs  a  circular  air-tight  pan 
provided  with  a  vertical  shaft  carrying  two  arms  which  are  curved  helically  in  a 
horizontal  plane.  The  arms  carry  sliding  teeth  which  rest  on  the  bottom  of  the 
pan,  and  the  shaft  may  be  rotated  in  either  direction  so  that  the  material  in  the 
pan  may  be  forced  outwards  or  inwards  as  desired.  The  raw  material  is  fed  into 
the  pan  from  a  valved  hopper,  a  reducing  gas  is  introduced  and  heat  is  applied  till 
water  ceases  to  be  evolved.  The  rotation  of  the  shaft  is  then  reversed,  and  the 
material  is  thereby  collected  towards  the  centre  of  the  pan  and  discharged  into  a 
well  or  seal  containing  oil. 

To  convert  finely  divided  metals  reduced  from  their  oxides  by  hydrogen,  into  a 
non-pyrophoric  condition  Edison  §  employs  a  current  of  nitrogen  or  other  inertgas 
to  displace  the  hydrogen.  On  removal  of  the  hydrogen  in  this  manner  the  metal 
may  be  exposed  to  the  air  without  danger  of  spontaneous  oxidation. 

Schwarcman  1 1  employs  a  catalyzer  of  nickel  incorporated  with  precipitated 
alumina  or  supported  on  a  carrier  of  fuller's  earth,  there  being  present  a  nitrogenous 
organic  colloid  such  as  wool.  For  example,  1  part  fuller's  earth  is  suspended  in 
5  parts  of  a  15  per  cent  caustic  soda  solution  and  boiled  for  one  hour.  The  earth 
is  then  washed,  placed  in  10  parts  of  water  and  1  part  of  nickel  nitrate  in  3  parts  of 
water  is  added.  After  boiling,  .275  parts  of  caustic  soda  and  .2  parts  wool  dissolved 
in  2.5  parts  water  are  introduced.  The  earth  and  precipitate  is  pressed,  dried  and 
reduced  in  hydrogen. 

KimuraH  heats  a  nickel  salt  on  a  carrier  of  asbestos  or  pumice,  in  an  atmosphere 
of  ammonia  gas  or  a  vaporized  ammonium  compound,  such  as  ammonium  chloride. 
The  catalytic  material  so  prepared  is  stated  to  be  active  at  a  relatively  low 
temperature. 

*  Chem.  Abs.,  1914,  3356;  French  Patent  No.  465,256,  November  24,  1913. 
t  British  Patent  No.  111.840,  November  5,  1917. 
j  British  Patent  115,924,  June  11,  1917;  J.  S.  C.  I.,  1918,  397  A. 
§  U.  S.  Patent  1,275,232,  August  13,  1918. 

||  U.  S.  Patents  1,172,062,  February  15,  1916;  1,280,314,  October  1,  1918.  Also  note 
1,111,502,  September  22,  1914. 

1f  J.  S.  C.  I.,  1918,  594  A;   British  Patent  118,323,  August  22,  1917. 


CHAPTER  VII 
THE  BASE  METALS  AS  CATALYZERS—Continued 

Wesson  *  prepares  a  catalyzer  by  first  dissolving  nickel  nitrate  in 
water  and  then  adding  ammonium  hydrate,  which  causes  nickel 
hydrate  to  be  precipitated  in  the  form  of  a  voluminous,  flocculent 
precipitate. 

Care  should  be  taken  to  add  only  a  sufficient  quantity  of  ammonium  hydrate 
to  form  the  precipitate,  as  an  excess  will  break  down  the  hydrate  of  nickel 
and  cause  it  to  re-dissolve.  In  thus  using  ammonia  as  a  precipitant,  sulphates 
or  chlorides  which  may  be  present  in  the  nickel  nitrate  will  be  converted  into 
sulphates  or  chlorides  of  ammonium  and  these  are  volatilized  at  the  tempera- 
ture at  which  the  nickel  is  subsequently  reduced.  This  serves  as  a  method  of 
purification,  which  is  very  desirable  in  order  to  produce  an  active  catalyzer. 
After  the  precipitate  of  hydrate  of  nickel  is  formed,  the  supernatant  liquid  con- 
taining ammonium  nitrate  and  some  unprecipitated  nickel  salts  may  be  de- 
canted off,  leaving  nickel  hydrate  and  water  with  a  sir  all  amount  of  ammonium 
salts  dissolved  in  the  water.  This  flocculent  precipitate  is  then  mixed  with  the 
inert  carrier  to  which  it  is  to  be  applied,  as,  for  instance,  asbestos.  The  pre- 
cipitate and  the  support  are  then  dried  to  expel  the  water  and  are  heated  at  a 
temperature  of  say  500°  C.  in  a  current  of  hydrogen  until  the  nickel  has  been 
reduced  to  a  finely-divided  condition,  covering  the  asbestos  fibers  or  other 
support  used.  The  ammonium  nitrate  that  remained  in  the  water  assists  in 
this.  As  the  support  covered  by  the  flocculent  precipitate  is  heated,  the  ammo- 
nium nitrate  is  decomposed,  leaving  most  of  the  nickel  hydrate  around  it  in 
a  very  fine  and  spongy  condition,  in  which  form  it  is  more  easily  reduced  by 
the  hydrogen,  and  at  the  same  time  the  operation  puts  it  in  such  shape  as  to 
present  a  greater  surface  for  contact  action. 

There  are  stated  to  be  substantial  advantages  in  applying  the  flocculent  hy- 
drate of  nickel  to  the  support,  instead  of  applying  to  the  support  a  solution  of 
a  salt  and  afterward  adding  a  precipitant.  For  in  the  former  case  the  hydrate 
acts  only  on  the  surface  of  the  support  (which  is  the  place  where  it  is  wanted) 
and  is  not  soaked  up  into  the  internal  pores  of  the  support,  as  it  would  be  if 
the  support  were  treated  with  a  solution  of  a  salt  and  precipitation  were  brought 
about  afterward. 

Nickel  hydrate  such  as  used  in  the  foregoing  (Wesson)  catalyzer 
is  prepared  according  to  Woodruff, f  in  the  following  manner: 

Nitrate  of  nickel  or  other  nickel  oxygen  salt  is  dissolved  in  sufficient  water  to 
form  a  dilute  solution,  which  should  contain  about  1  per  cent  of  the  crystalline 

*U.  8.  Patent  No.  1,143,339,  June  15,  1915. 

fU.  S.  Patent  No.  1,143,343,  June  15,  1915. 

172 


THE  BASE   METALS  AS  CATALYZERS  173 

salt,  and  the  solution  is  then  brought  to  a  temperature  in  the  neighborhood  of 
the  boiling-point.  Satisfactory  results  are  obtained  at  a  temperature  of  ap- 
proximately 95°  C.  Sufficient  hydroxide  of  ammonium  to  theoretically  precip- 
itate all  the  nickel  present  is  then  added.  In  practice  an  ammonium  hydroxide 
solution  of  a  specific  gravity  of  about  26°  Baume  is  used.  The  correct  amount 
of  a  given  solution  of  the  ammonium  hydroxide  to  add  to  the  solution  of  the 
nickel  salt  may  be  determined  by  slowly  adding  the  ammonia  to  a  small  quan- 
tity of  the  nickel  solution  under  the  above  conditions,  and  noting  the  point  at 
which  the  precipitate  commences  to  dissolve.  A  slightly  smaller  proportion  of 
ammonia  should  then  be  added  to  the  bulk  of  the  nickel  solution.  Under  these 
conditions  it  will  be  found  that  practically  all  the  nickel  will  be  precipitated  in 
the  form  of  flocculent  nickel  hydroxide.  If  a  more  concentrated  nickel  solution 
be  employed  or  if  precipitation  be  brought  about  at  a  lower  temperature  or  if 
an  excess  of  ammonia  be  added,  the  amount  of  nickel  thrown  down  will  be  rela- 
tively decreased. 

After  the  nickel  hydroxide  is  precipitated  it  may  be  applied  to  a  support  while 
still  in  the  solution  in  which  it  was  formed,  or  the  supernatant  liquid  may  be 
decanted  off.  By  the  use  of  a  very  dilute  solution  of  the  nickel  salt  from  which 
the  precipitate  is  formed,  practically  all  of  the  impurities  are  said  to  be  removed, 
when  the  supernatant  liquid  is  decanted  off,  whether  before  or  after  the  applica- 
tion of  the  precipitate  to  the  support,  thus  eliminating  the  necessity  of  washing 
the  catalyzer.  The  precipitate  and  the  support  are  then  dried  to  expel  water 
and  are  heated  to  a  temperature  of  about  500°  C.  in  a  current  of  hydrogen. 

In  accordance  with  a  method  of  the  Badische  Co.*  a  complex, 
insoluble  compound  containing  one  or  more  easily  replaceable  bases, 
e.g.,  an  artificial  silicate  such  as  sodium  aluminate-silicate  '("  Per- 
mutit  "),  is  treated  with  a  salt  of  a  catalytic  metal  such  as  palladium, 
nickel,  copper,  zinc,  or  vanadium,  and  the  salt  reduced  with  hydro- 
gen. The  catalytic  agents  thus  produced  may  be  used  for  the 
hardening  of  oils,  the  hydrogenation  or  dehydrogenation  of  organic 
compounds,  etc.f 

For  treating  carbon  compounds  with  hydrogen  in  the  presence  of 
catalyzers  the  Badische  Co.J  employ  a  contact  mass  composed  of  a 
catalytic  base  metal  in  intimate  contact  with  silica,  shaped  as 
desired. 

Carborundum,  clay,  carbon,  alumina,  kaolin,  amorphous  silica,  and  other  sub- 
stances in  a  finely-divided  condition,  are  capable  of  adsorbing  colloidal  metals, 
forming  bodies  which  may  be  used  as  catalysts,  medicinal  powders,  etc.  The 
substance  which  is  to  serve  as  adsorbent  may  be  brought  into  a  state  of  sol- 
suspension  in  water  or  other  suitable  liquid,  a  solution  of  a  metallic  salt  added, 
and  the  metal  precipitated  by  reduction.  § 

*J.  S.  C.  I.,  1915,  822. 

t  See  also  British  Patent  No.  1,358,  January  27,  1915;  U.  S.  Patent  No.  1,256,032, 
February  12,  1918;  Chem.  Abs.,  1918,  1006. 

J  Swiss  Patent  No.  72,689,  June  16,  1916;    Chem.  Abs.,  1916,  2625. 

§Ges.  f.  Elektro-osmose  G.  m.b.  H.  German  Patent  No.  252,372,  January  9,  1912; 
J.  8.  C.  I.,  1912,  1201. 


174  THE  HYDROGENATION  OF  OILS 

A  nickel  adsorption  suitable  for  use  as  a  catalyst  is  prepared  by  subjecting 
an  aqueous  suspension  of  silicic  acid  to  the  action  of  an  electric  arc  between 
nickel  electrodes.* 

Richardson  f  prepares  a  finely-divided  catalytic  metal  by  electrical 
disintegration,  as  follows: 

Two  pieces  of  a  suitable  metal  are  submerged  in  ether  or  other  fat  solvent 
and  an  electric  current  is  sent  through  the  pieces  which  serve  as  electrodes, 
these  being  spaced  apart  and  provided  with  sufficient  current  to  produce  an 
electric  arc  across  the  gap  between  them,  and  to  cause  part  of  the  metal  of  the 
electrodes  to  disintegrate  and  become  diffused  in  finely-divided  form  or  in  col- 
loidal solution  or  suspension  in  the  fat  solvent,  forming  an  organosol.  The 
electrodes  may  be  nickel,  copper,  platinum,  palladium,  iron,  or  their  alloys. 
They  may  be  conveniently  used  in  the  form  of  rods  and  the  electric  current 
may  be  operated  by  a  hand  feed  or  automatic  arc  lamp  mechanism  in  which 
the  rods  are  clamped.  The  electric  current  (preferably  direct)  is  operated  at  a 
voltage  of  from  40  to  150.  The  arc  is  allowed  to  continue  until  the  desired 
amount  of  disintegrated  or  finely-divided  metal  has  been  produced  in  the  fat 
solvent.  The  metal  and  fat  solvent  are  then  separated,  as  may  be  done  by 
settling,  filtering,  or  heating  until  the  fat  solvent  has  evaporated.  The  remain- 
ing disintegrated  metal  is  a  highly  active  catalyst,  well  adapted  for  hydrogenating 
oils.  This  preparation  is  then  mixed  with  the  mass  of  oil  to  be  hydrogenated, 
in  the  proportion  of  about  1  to  3  per  cent  of  the  metal  to  the  mixture,  by 
weight.  The  mixing  is  done  while  hydrogen  gas  or  gas  containing  hydrogen  is 
introduced  into  the  mixture,  and  the  hydrogenating  treatment  is  preferably 
done  under  heat  and  pressure. 

When  operating  under  about  40  Ib.  pressure  and  with  a  temperature  of  about 
160°  C.,  the  process  of  hardening  or  solidifying  of  the  oil  or  fat  may  be  com- 
pleted in  from  one  to  eight  hours,  depending  upon  the  percentage  of  the  finely- 
divided  metal  used,  the  kind  of  fat  or  oil  being  hardened,  the  rapidity  of  agita- 
tion, etc.,  and  upon  the  degree  of  hardness  desired,  t 

Ellis  §  comminutes  nickel  electrically  by  forming  an  arc  between 
nickel  electrodes  under  water  and  levigates  to  separate  light  from 
heavy  nickel  particles.  The  sludge  of  light  material  is  collected  and 
heated  with  oil  to  expel  moisture. 

Elworthy  ||  prepares  nickel  adherent  to  the  surface  of  fire  brick,  pumice  or 
asbestos  fiber  and  the  product  agglutinated,  to  form  catalytic  material. 

Aluminum,  glass  and  ceramic  surfaces  are  coated  with  nickel  and  other 
metals  by  immersing  the  articles  in  the  heated  metal  salt  solution  which  con- 
tains ammonia  and  alkali  phosphites  or  hypophosphites.  H 

*  British  Patent  No.  15,267,  June  25,  1914,  J.  S.  C.  I.,  1915,  803  and  1913,  842. 

fU.  S.  Patent  No.  1,151,045,  August  24,  1915. 

J  See  also  U.  S.  Patent  No.  1,175,905,  March  14,  1916;  No.  1,177,896,  April  4,  1916; 
No.  1,257,396,  No.  1,257,397,  No.  1,257,531,  February  26,  1918. 

§U.  S.  Patent  No.  1,092,206,  April  7,  1914. 

||  U.  S.  Patent  No.  943,627,, December  14,  1909. 

1  L' Aluminum  Francaia;  French  Patent  No.  464,721,  January  20,  1913;  Chem. 
Abs.,  1915,  1376. 


THE  BASE   METALS  AS  CATALYZERS  175 

The  Oelverwertung  G.  m.  b.  H.  describe  a  process  of  manufactur- 
ing catalytic  bodies,  for  use  in  effecting  reactions  in  liquids  and  gases, 
consisting  in  heating  (thermolyzing)  a  compound  of  a  metallic  nitrate 
and  a  soluble  organic  compound  such  as  sugar.  (See  page  199.) 
The  resulting  voluminous  product  is  reduced  by  hydrogen  at  200° 
to  300°,  a  finely-divided  and  highly  active  metal  powder  being 
obtained.* 

The  Badische  Co.f  propose  the  treatment  of  fatty  acids  and  esters 
with  nickel,  cobalt  or  iron  catalyzer  under  a  hydrogen  pressure  of 
at  least  thirty  and  preferably  of  fifty  atmospheres  while  operating 
continuously. 

A  catalyzer  for  oil  hardening  recommended  by  the  author  J  is 
prepared  by  electrolyzing  a  nickel  solution  to  form  nickel  in  a  highly 
extended  condition,  so  that  a  relatively  large  surface  is  exposed 
enabling  a  small  amount  of  catalyzer  to  serve  in  hardening  a  large 
amount  of  oil.  The  nickel  may  be  deposited  independently  or  on  a 
carbonaceous  body  such  as  finely-divided  graphite  or  charcoal. 

A  form  of  nickel  catalyzer  was  prepared  in  the  author's  labora- 
tory by  decomposing  silicon  tetrafluoride  with  water  which  yielded  a 
very  voluminous  form  of  silica. 

This  material  was  carefully  washed  free  from  chlorides  and  sulphates  and 
dried.  An  amount  of  nickel  nitrate  crystals  equal  in  weight  to  the  silica  was 
dissolved  in  five  parts  of  water  and  the  solution  was  thoroughly  mixed  with  the 
silica.  The  mixture  was  dried  and  ignited  until  all  fumes  of  nitrogen  oxides 
were  expelled.  The  dark  powdery  material  was  heated  in  a  current  of  hydrogen 
for  one  hour  at  327°  C.,  cooled  and  preserved  under  oil  to  prevent  oxidation. 
This  material  carried  approximately  one-sixth  of  its  weight  of  nickel.  To  a 
quantity  of  cottonseed  oil,  an  amount  of  this  catalyzer  was  added  to  introduce 
0.7  per  cent  of  nickel  and  hydrogen  was  passed  through  the  oil  and  catalyzer 
for  2 \  hours  at  175°  C.  At  the  end  of  this  time  the  hardened  fat  produced 
was  found  to  have  an  iodine  number  of  29.8. 

Sabatier  and  Espil§  have  found  nickel  reduced  from  the  oxide  at 
temperatures  above  350°  C.  is  capable  of  hydrogenating  the  benzol 
ring.  Frequent  assertions  have  previously  been  made  to  the  con- 
trary. Sabatier  and  Espil  find  that  nickel  reduced  at  500°  and  main- 
tained for  eight  hours  at  500°  to  700°  in  an  atmosphere  of  hydrogen 
is  still  active  in  this  respect.  When  heated  to  750°  it  would  no 

*  Italian  Patent  No.  130,394;  March  13,  1913.  See  also  Austrian  Patent  70,930, 
Jan.  10,  1916;  Chem.  Abs.,  1916,  1279. 

t  German  Patent  Application  No.  73,304,  Seifen.  Ztg.,  1915,  349. 
tU.  S.  Patent  No.   1,151,003,  August  24,   1915. 
§Bull.  Soc.  Chim.,  Vol.  XV.,  1914,  779. 


176  THE  HYDROGENATION  OF  OILS 

longer  act  to   carry  hydrogen   to   the   benzol  ring  although   it   was 
still  capable  of  effecting  the  reduction  of  nitro  bodies. 

Bacon  and  Nicolet  *  prepare  a  catalyzer  by  impregnating  an  inert, 
porous  supporting  material  or  carrier,  preferably  pulverulent,  such 
as  kieselguhr,  or  powdered  pumice,  with  a  precipitant  for  a  nickel 
salt. 

Such  precipitant  may  be  any  suitable  hydroxide  or  carbonate,  such  as  sodium 
hydroxide  associated  with  a  small  quantity  of  a  substance  which  will  give  a  bulky 
precipitate  simultaneously  with  the  precipitation  of  the  nickel  salt.  This  sup- 
plemental substance  may  be,  for  example,  sodium  aluminate,  and  the  bulky 
precipitate  therefrom  will  in  such  case  be  aluminum  hydroxide.  To  the  sup- 
port or  carrier  thus  impregnated  with  the  precipitant  for  nickel  and  the  sup- 
plemental precipitant,  is  added  a  solution  of  an  appropriate  soluble  nickel  salt, 
as,  for  instance,  the  nitrate.  Thereupon,  the  nickel  salt  is  precipitated  as  nickel 
hydroxide  by  the  sodium  hydroxide  or  its  equivalent  upon  and  within  the 
catalyst.  At  the  same  time,  there  is  simultaneously  precipitated  the  supple- 
mental bulky  material  by  the  decomposition  of  the  sodium  aluminate.  This 
supplemental  bulky  material  (in  this  case,  aluminum  hydroxide)  further  increases 
the  surface  of  exposure  of  the  catalyst.  The  impregnated  support  or  carrier  is 
then  washed  to  remove  any  injurious  soluble  products  that  may  be  present, 
and  is  thereafter  dried  and  the  insoluble  nickel  salt  reduced  to  catalytically 
active  nickel,  at  a  temperature  which  preferably  should  not  exceed  a  range  of 
from  350°  C.  to  450°  C.  and  with  a  duration  of  treatment  of  from  one  to  two 
hours.  If  the  solution  of  the  nickel  salt  is  absorbed  by  the  support,  and  the 
product  so  obtained  made  to  react  with  the  solution  of  aluminate  and  other 
precipitant,  less  effective  results  are  obtained. 

As  an  example  of  the  manner  of  carrying  out  the  process,  100  Ib.  of  the  de- 
sired carrier,  say  pumice  stone  in  small  fragments,  is  impregnated  with  a  solu- 
tion containing  65  Ib.  sodium  hydroxide  and  sodium  aluminate  equivalent  to 
5  Ib.  aluminum  oxide;  the  precipitating  solution  containing  165  Ib.  crystallized 
nickel  nitrate.  The  product  is  filtered,  washed  to  remove  soluble  salts,  or  most 
of  them,  and  reduced  for  two  hours,  between  350°  C.  and  450°  C.  The  catalyst 
made  as  described  should  contain  about  25  per  cent  nickel,  and  about  5  per  cent 
aluminum  oxide. 

Fragments  of  glass  coated  with  about  1  per  cent  of  their  weight 
of  reduced  nickel  are  recommended  by  Wells  f  as  catalytic  material. 
The  hydrogenation  of  the  unsaturated  components  of  light  petro- 
leum oils  has  been  carried  out  by  passage  of  the  oil  vapors  through 
a  column  of  contact  material  composed  of  nickel-coated  glass  frag- 
ments about  0.5  in.  in  diameter. 

Sulzberger  J  finds  the  reducing  power  of  hydrazine  on  metal  com- 
pounds is  increased  in  the  presence  of  a  metal  of  the  platinum  group, 
which  may  be  added  in  the  form  of  a  sol.  A  nickel  compound  thus 

*  U.  S.  Patent,  No.  1,152,591,  September  7,  1915. 

fU.  S.  Patent  No.  1,179,484,  April  18,  1916;    J.  S.  C.  I.,  1916,  623. 

j  Canadian  Patent  No.  181,447,  Jan  1,  1918;  Chem.  Abs.,  1918,  605. 


THE  BASE  METALS  AS  CATALYZERS  177 

treated  produces  a  black  non-pyrophoric  powder  which  contains  nickel, 
and  the  metal  of  the  platinum  group  is  an  intimate  mixture. 

Various  methods  of  utilizing  nickel  carbonyl  as  a  catalyzer  in  oil 
hardening  are  described  by  the  author.* 

The  nickel  compound  is  brought  into  contact  with  heated  oil  with  or  without 
pressure  to  decompose  the  carbonyl  and  liberate  finely-divided  nickel.  A  mix- 
ture of  nickel  carbonyl  and  hydrogen  may  be  passed  into  the  oil  to  be  hydro- 
genated  liberating  nickel  in  a  nascent  condition  in  the  presence  of  hydrogen. 
Satisfactory  results  have  been  secured  in  the  author's  laboratory  by  passing 
nickel  carbonyl  vapors  into  cottonseed  oil  at  a  temperature  of  about  200°  C. 
until  a  sufficient  amount  of  nickel  had  been  formed  to  exert  the  desired  rate  of 
catalytic  action.  The  oil  is  then  cooled  to  about  180°  C.,  and  hydrogen  intro- 
duced. Hydrogenation  readily  takes  place  under  these  conditions  even  with 
only  ^  or  1%  of  a  per  cent  of  nickel  present, 

NICKEL  SILICATE 

Byrom  f  prepares  a  catalyst  by  precipitating  a  nickel  salt  from 
solution  by  means  of  an  alkali  silicate. 

For  example,  he  takes  10  Ib.  of  nickel  sulphate,  pure  and  free  from  arsenic, 
and  dissolves  this  salt  in  boiling  water  to  form  a  saturated  solution.  Twenty 
pounds  of  a  solution  of  sodium  silicate  (alkaline  glass t)  of  100°  Twaddle  are  added 
and  reduced  to  25°  Twaddle  with  boiling  water;  the  solution  being  stirred  until 
the  whole  of  the  sodium  silicate  solution  has  been  added.  The  precipitate 
thus  formed  is  transferred  to  a  filter  and  is  washed  with  boiling  water  until  the 
filtrate  is  free  from  sodium  sulphate.  The  precipitate  is  pressed  to  free  from 
excess  of  water.  The  operation  of  filtering  may  be  carried  out  by  the  use 
of  a  filter  press  and  the  combined  nickel  hydroxide  and  silicic  acid  is  thus  ob- 
tained in  the  form  of  cakes  which,  when  dry,  is  porous  and  can  then  be  ground 
to  a  fine  powder.  The  product  may  be  used  direct  as  a  catalyst,  or  it  may  be 
reduced  to  the  metallic  state  by  heating  in  a  current  of  hydrogen  at  as  low  a 
temperature  as  possible  until  no  water  vapor  is  given  off.  A  temperature  of 
300°  C.  is  stated  to  be  sufficient  for  complete  reduction.  Produced  as  described 
the  catalyst  will  contain  about  21  per  cent  of  metallic  nickel,  and  in  use  for  the 
treatment  of  oils,  and  fats  from  \  to  1  per  cent  of  catalyst  will  be  required 
calculated  on  the  percentage  of  nickel  it  contains. 

Byrom  observes  that  the  preparation  of  catalysts  by  impregnating  inert 
substances  such  as  kieselguhr,  with  a  solution  of  a  metallic  salt,  and  precipitating 
the  hydroxide  or  carbonate  on  the  inert  substance  by  adding  the  required  amount 
of  a  solution  of  the  alkali  hydrates,  or  carbonates,  give  products  which  are  dif- 
ficult to  filter  and  purify.  In  the  case  of  impregnating  kieselguhr  with  a  solu- 
tion of  nickel  sulphate  and  forming  nickel  hydroxide  by  adding  a  solution  of 
sodium  hydrate,  the  precipitate  formed  is  stated  to  be  extremely  difficult  to 

*  U.  S.  Patent  No.  1,138,201,  May  4,  1915  and  1,154,495,  September  21,  1915. 
t  British  Patent  No.   13,382,   1913. 

J  Sodium  silicate  is  manufactured  in  two  qualities  known  as  alkaline  glass  and 
neutral  glass. 


178  THE  HYDROGENATION  OF  OILS 

purify  and  filter  so  as  to  obtain  the  product  free  from  sodium  sulphate  formed 
in  the  mother  liquid. 

By  Byrom's  method,  it  is  possible  to  increase  the  size  of  the  grains  in  the 
precipitate,  by  allowing  the  deposited  material  to  stand  for  a  few  hours  in  the 
solution  at  a  temperature  of  80°  C.  or  thereabouts,  as  the  dissolved  inorganic 
salt  (sodium  sulphate)  precipitates  the  gelatinous  matter  in  the  form  of  flakes, 
and  for  the  time  being  prevents  the  formation  of  a  colloidal  solution,  and,  con- 
sequently allows  rapid  filtration  until  the  precipitate  is  free  from  sulphate  and 
impurities.  As  soon  as  the  precipitate  is  free  from  the  dissolved  inorganic  salt 
it  commences  to  be  difficult  to  filter,  as  a  colloidal  or  pseudo  solution  is  formed, 
which  passes  through  the  filter,  and  this  is  taken  as  an  indication  that  the  pre- 
cipitate is  free  from  sulphates  and  impurities.  Byrom  has  found  that  the 
catalyst  prepared  as  above  described  after  drying  may  be  used  with  advantage 
in  the  hydrogenation  of  oils  without  being  reduced  to  the  metallic  state.  He 
notes  that  the  metallic  hydroxide  and  silicic  acid  on  being  heated  to  a  tempera- 
ture over  110°  C.  lose  the  property  of  forming  colloidal  solutions,  being  trans- 
formed into  the  crystalloids,  the  grains  of  which  are  much  larger,  and  that 
nickel  thus  obtained  in  combination  with  the  silica  acts  as  a  catalyst,  and  the 
hydrogenation  proceeds  with  greater  velocity,  than  with  the  fully-reduced  cata- 
lyst. 

Byrom  also  proposes  to  use  a  solution  containing  9  Ib.  of  nickel  sulphate  and 
1  Ib.  of  titanous  sulphate  and  thus  to  produce  a  mixture  of  oxides  along  with  the 
silica. 

The  silica  in  combination  with  the  metallic  oxide  or  metal  exerts  a  decolorizing 
action  on  the  oils  treated,  and  facilitates  the  separation  of  the  catalyst  from  the 
treated  product. 

Byrom  does  not  indicate  to  what  extent  nickel  is  present  as  the  silicate  or 
what  proportion  of  free  oxide  or  metal  exists  in  the  finished  material. 

Instead  of  supporting  a  catalytic  metal  on  a  carrier  of  kieselguhr, 
kaolin  or  asbestos  Sulzberger  *  states  he  has  found  that  a  much 
simpler  method  of  finely  dividing  and  spreading  a  catalytically 
efficient  substance  over  an  inert  material  containing  silicon,  silica 
or  other  compounds  containing  silicon  as  follows: 

An  aqueous  solution  of  a  nickel  salt  is  treated  with  a  solution  of  sodium  sili- 
cate, the  precipitate  filtered  off,  dried  and  subjected  to  a  current  of  hydrogen, 
while  being  heated.  A  black  powder  is  obtained.  This  substance  is  used  as  a 
catalyzer,  in  hydrogenating  oils,  with  which  it  can  readily  be  mixed,  remaining 
well  in  suspension.  It  is  stated  that  the  latter  effect  may  be  due  to  silicic  acid 
in  a  colloidal  condition,  f 

Sulzberger  also  recommends  |  borates,  titanates,  chromates,  and 
uranates,  of  metals  such  as  nickel,  palladium  or  platinum.  In 

*U.  S.  Patent  No.  1,143,332,  June  15,  1915  and  Reissue  Patent  No.  14,167, 
July  18,  1916. 

fJ.  S.C.I.,  1915,822. 

}  British  Patent  No.  8,130,  June  1,  1916;  Canadian  Patent,  No.  181,287,  December 
25,  1917;  Chem.  Abs.,  1918,  605. 


THE  BASE  METALS  AS  CATALYZERS  179 

most  cases  the  catalysts  are  formed  by  reduction.  E.g.,  a  solution 
of  nickel  chloride  is  treated  with  sodium  silicate  to  precipitate  nickel 
silicate,  which  is  reduced  in  hydrogen  at  a  low  temperature  to  give  a 
nickel  catalyst.  If  a  small  amount  of  a  palladium  salt  is  added  to 
the  solution  of  nickel  chloride,  the  resulting  catalyst  is  rendered 
more  active.  These  catalysts  may  be  used  in  the  hydrogenation  of 
cottonseed  oil. 

The  regeneration  of  a  spent  nickel  silicate  catalyzer  of  the  type 
described  above  is  carried  out  by  Sulzberger  *  as  follows: 

The  catalyst  is  largely  separated  from  the  oil  or  other  substance  which  has 
been  hydrogenated  and  the  residue  of  the  latter  is  removed  by  extraction  or 
calcination.  The  catalyzer  is  then  treated  with  the  minimum  requisite  propor- 
tion of  caustic  soda  to  dissolve  the  silica  (or  boric  acid,  if  nickel  borate  has  been 
used)  yielding  the  alkali  salt.  This  solution  is  separated  from  the  residual  matter 
containing  nickel  and  the  latter  is  dissolved  in  an  acid,  nitric  acid  being  recom- 
mended for  the  purpose.  The  acid  and  alkali  solutions  are  mixed  and  nickel 
silicate  is  again  formed.  The  precipitate  is  washed  to  free  from  soluble  salts 
and  is  then  reduced  in  an  atmosphere  of  hydrogen  gas.  Other  metal  com- 
pounds including  those  of  copper,  titanium  and  uranium  silicate  or  borate  are 

stated  to  be  capable  of  regeneration  in  a  similar  manner. 

'  / 

The  use  of  non-abrasive  silica  in  conjunction  with  nickel  and  with  or  without 
palladium  is  proposed  by  Ellis,  f  The  silica  may  be  prepared  by  passing  silicon 
tetrafluoride  into  water,  collecting  and  drying  the  precipitated  silicious  material 
and  incorporating  with  a  nickel  salt  or  palladium  compound. 

NICKEL  BORATE 

Schoenfeld  J  observes  that  oil  hardening  with  the  organic  salts  of 
nickel  such  as  nickel  formate  and  acetate  is  a  special  case  of  hydro- 
genation by  means  of  metallic  nickel,  as  these  organic  salts  at  the 
high  temperature  employed  and  under  the  influence  of  hydrogen  are 
reduced  to  the  metallic  state  when  catalytic  action  becomes  manifest. 
Schoenfeld  has  investigated  the  catalytic  properties  of  an  inorganic 
salt  of  nickel,  namely,  nickel  borate,  and  advises  that  this  compound 
is  active  as  hydrogen  carrier  for  oils  and  that  it  does  not  become 
reduced  during  the  hydrogenation  treatment. 

The  nickel  borate  which  Schoenfeld  used  was  obtained  from  Kahlbaum.  The 
salt  was  of  a  greenish  color,  insoluble  in  water,  but  soluble  in  acetic  acid  and 
dilute  mineral  acids.  On  heating  strongly  the  color  changed  to  a  greenish- 
yellow.  In  order  to  improve  the  catalytic  activity  Schoenfeld  found  it  advan- 
tageous to  heat  the  borate  at  300°  C.  in  an  atmosphere  of  hydrogen.  By  this 

*  U.  S.  Patent  No.  1,199,032,  September  19,  1916. 
fU.  S.  Patent  No.  1,266,782,  May  21,  1918. 
JSiefen.  Ztg.,  1914,  945. 


180  THE  HYDROGENATION  OF  OILS 

treatment  a  large  part  of  the  water  of  crystallization  was  lost  but  otherwise 
apparently  no  chemical  change  took  place  in  the  borate.  Schoenfeld  notes  that 
the  removal  of  the  water  is  of  importance  in  connection  with  the  oil  hardening 
for  if  the  water-containing  salt  is  applied  directly,  a  greater  part  of  the  water 
is  lost  during  hydrogenation  and  because  of  this  change  the  catalyzer  forms  lumps 
which  do  not  distribute  well  through  the  oil.  Furthermore  a  higher  temperature 
is  required  when  water-containing  borate  is  directly  employed  as  a  catalyzer. 
To  remove  the  water  Schoenfeld  heated  the  borate  in  hydrogen  for  one-half  hour  at 
300°  C.  in  an  electrically-heated  glass  tube.  The  product  so  obtained  was  of  a 
dark  grey  color.  After  such  heating  analysis  showed  the  following  composition: 

NiO 44.73% 

B203 42.01% 

Calculated  for  NiB2O4-H2O. 

NiO 45.9% 

B203 43.0% 

These  results,  therefore,  indicate  the  compound  to  be  nickel  metaborate  con- 
taining 1  molecule  of  water  of  crystallization.  The  remaining  water  of  crys- 
tallization may  be  removed  by  protracted  heating  at  300°.  For  technical  appli- 
cation it  is  not  necessary,  however,  to  remove  all  the  water,  as  the  activity  of 
the  catalyzer  is  not  increased  by  such  protracted  heat  treatment. 

The  catalytic  activity  of  the  compound  was  determined  in  the  following  simple 
manner: 

One  hundred  to  200  g.  of  the  oil  with  1  per  cent  of  the  nickel  borate  were 
placed  in  a  flask  of  about  \  liter  capacity  and  were  heated  to  160°  to  180°  C. 
while  hydrogen  was  passed  through  the  oil.  After  the  hydrogen  was  introduced 
in  this  manner  for  a  short  time  the  contents  of  the  flask  acquired  a  greyish  color 
as  the  result  of  the  fine  distribution  of  the  catalyzer  in  the  oil  Hydrogen  was 
applied  for  2^  to  three  hours  and  the  oil  then  filtered  through  paper.  The 
residue  of  the  ca  alyzer  was  extracted  with  ether  and  benzene  until  supposedly 
free  from  oil,  but  on  treatment  with  dilute  mineral  acids,  oily  drops  separated. 
It  was,  therefore,  concluded  that  during  the  hardening  some  of  the  free  fatty 
acid  present  in  the  oil  combined  with  nickel,  forming  a  metallic  soap  with  liber- 
ation of  boric  acid.  To  ascertain  if  this  were  the  case  5  g.  of  the  used  cata!y:er 
were  dissolved  in  dilute  hydrochloric  acid  and  the  oil  which  separated  was 
extracted  with  ether  and  purified.  The  oil  obtained  was  yellowish  in  color  and 
contained  about  50  per  cent  of  free  fatty  acid  corresponding  to  an  acid  number 
of  98.  The  acid  number  of  the  original  oil  was  0.3.  After  the  hardening  opera- 
tion the  nickel  borate  was  found  to  contain  less  boric  acid  than  corresponded 
to  the  original  formula. 

ANALYSIS  OF  NICKEL  BORATE  USED  FOR  HARDENING 

NiO  B2Os 

1.  Used  once 42.07  28.3 

2.  Used  twice 44.3  33.84 

3.  (a)  Used  once 43.5  34.9 

(6)  Used  twice 43.88  33.5 

(c)  Used  three  times 45.5  29.42 

In  investigation  (3)  an  endeavor  was  made,  by  careful  drying  of  the  hydrogen 
to  reduce  the  formation  of  fatty  acid  to  a  minimum.  The  same  mass  of  cata- 


THE  BASE  METALS  AS   CATALYZERS  181 

lyzer  was  used  four  to  six  times  for  hardening  without  any  diminution  of  its 
activity.  From  the  following  observations  Schoenfeld  concluded  that  catalysis 
was  due  to  nickel  borate  alone  and  not  to  the  small  amount  of  nickel  soap  pres- 
ent for  the  reason  that  (1)  the  temperature  of  160°  to  180°  was  regarded  as 
insufficient  to  cause  nickel  soap  to  become  active;  (2)  the  amount  of  the  latter 
was  too  slight  to  effect  any  considerable  change,  and  (3)  if  the  nickel  soap  were 
responsible  for  hydrogen  addition  the  activity  of  the  nickel  borate  catalyzer 
would  increase  with  repeated  use  as  a  result  of  the  increase  in  the  amount  of 
nickel  soap.  Schoenfeld  found  that  as  the  content  of  nickel  borate  is  reduced 
the  activity  of  the  catalyzer  correspondingly  diminishes.  Various  oils  were 
treated  with  the  borate  catalyzer,  including  cottonseed,  rape,  linseed,  soya  bean 
and  whale  oil,  and  satisfactorily  hardened  products  obtained.  In  one  experi- 
ment made  by  Schoenfeld  200  g.  of  cottonseed  oil  were  mixed  with  2  g.  of  nickel 
borate  add  heated  for  three  hours  at  160  to  170°  in  a  stream  of  hydrogen.  The 
solidifying  point  of  the  hardened  oil  was  38°  C.  By  longer  action  of  the  hydrogen 
a  solidifying  point  of  47°  was  obtained.  The  application  of  pressures  of  one-half 
to  one  atmosphere  somewhat  improved  the  reaction  so  that  in  two  hours  linseed  oil, 
for  example,  was  converted  into  a  fat  of  the  consistency  of  tallow  with  a  solidify- 
ing-point  of  38°.  The  hardened  oils  which  Schoenfeld  prepared  by  means  of 
nickel  borate  possessed  a  pure  white  color  and  the  acid  number  was  not  increased 
by  the  hardening  treatment.  Schoenfeld  regards  nickel  borate  especially  desirable 
as  a  catalyzer  because  it  appears  that  the  ordinary  catalyzer  poisons  such  as  sulphur 
do  not  effect  the  activity  of  the  borate.  Schoenfeld  in  fact  added  sulphur  to 
cottonseed  oil  and  claims  no  detrimental  effect  was  incurred  thereby.  He  sum- 
marizes the  advantages  of  using  nickel  borate,  as  follows:  The  hardening  occurs 
at  a  relatively  low  temperature  (160°  to  180°  and  in  most  cases  between  160° 
to  170°).  The  application  of  gas  under  pressure  is  not  necessary,  and  the 
hydrogenation  can  be  carried  out  in  very  simple  apparatus.  The  lack  of  sensi- 
tiveness to  catalyzer  poisons  and  the  ability  to  use  the  nickel  borate  repeatedly 
also  are  advantages. 

Erdmann  and  Rack  *  carried  out  various  tests  with  nickel  borate 
which  lead  them  to  regard  Schoenfeld's  conclusions  as  unreliable. 

It  was  noted  that  Schoenfeld  used  Kahlbaum's  nickel  borate  containing  slightly 
more  nickel  than  corresponded  to  the  formula  NiO-B2O3  on  linseed  oil  and  also 
on  the  easiest  of  all  fatty  oils  to  harden,  i.e.,  refined  cotton  oil. 

No  hydrogenating  action  was  observed  with  either  hydrated  or  anhydrous 
nickel  borate  at  a  temperature  of  175°  C.  Green  nickel  borate  was  heated  for 
one-half  hour  at  330°  to  340°  C.,  in  a  stream  of  nitrogen.  Four  grams  of  this 
borate  material  was  introduced  into  400  g.  of  cotton  oil  which  previously  had 
been  heated  to  100°  C.  The  temperature  was  raised  to  175°  C.  and  a  stream 
of  hydrogen  at  the  rate  of  20  liters  per  minute  was  passed  through  the  oil  for 
three  hours.  No  hardening  occurred.  Linseed  oil  gave  the  same  results. 

Green  nickel  borate  was  heated  in  hydrogen  at  300°  to  305°  C.  for  one-half 
hour,  and  during  this  treatment  the  color  of  the  material  changed  from  yellowish 
brown  to  grey.  An  aqueous  solution  of  phosphomolybdic  acid  was  colored  blue 
on  standing  with  some  of  the  grey  product.  Cotton  oil  treated  for  9|  hours 

*Seifen.  Ztg.,  1915,  3. 


182  THE  HYDROGENATION  OF  OILS 

with  this  hydrogen  treated  material  hydrogenated  only  slightly  indicating  very 
weak  hydrogenating  power. 

A  quantity  of  the  borate  was  exposed  to  hydrogen  at  a  temperature  of  340° 
and  a  dark  grey  product  obtained.  Under  the  same  conditions  except  in  an 
atmosphere  of  nitrogen  a  yellowish  brown  material  resulted.  While  the  latter 
material  was  neither  magnetic  nor  reactive  with  phosphomolybdic  acid,  the  dark 
grey  product  was  attracted  by  a  magnet  and  colored  phosphomolybdic  acid 
strongly  blue.  Some  of  the  grey  product  was  pressed  to  form  a  block  and  a 
current  of  electricity  at  80  volts  used  to  test  its  electrical  conductivity.  No 
passage  of  the  current  could  be  detected  when  employing  a  sensitive  milliampere 
meter,  from  which  Erdmann  concluded  that  no  metallic  nickel,  but  nickel  sub- 
oxide,  was  present.  On  treatment  with  dilute  mineral  acid  hydrogen  was  evolved 
in  an  amount  corresponding  to  7.4  per  cent  nickel  suboxide  (Ni2O). 

Four  grams  of  the  dark  grey  product  were  mixed  with  400  g.  of  edible  cotton 
oil  and  on  heating  to  175°  to  180°  C.,  a  hydrogen  stream  (20  liters  per  minute) 
was  passed  through  the  oil  for  three  hours  when  the  solidifying  point  of  the 
latter  was  found  to  be  31.8°  C.  The  catalyzer  distributed  well  through  the  oil 
in  the  manner  characteristic  of  nickel  suboxide  and  due,  it  is  stated,  to  the 
formation  of  an  organosol.  The  recovered  catalytic  agent  did  not  exhibit  any 
electrical  conductivity. 

Five  hundred  grams  of  cotton  oil  were  heated  to  125°  C.,  15  g.  green  nickel 
borate  were  added  and  the  temperature  was  then  raised  to  260°.  A  stream  of 
hydrogen  was  passed  through  the  oil  for  five  hours,  and  the  oil  was  found  to 
be  hydrogenated  to  a  solidifying  point  of  31.8°. 

As  is  known,  boric  acid  is  a  very  weak  acid  body  and  the  salts  of  mono-  and 
tri-basic  boric  acid  are,  therefore,  very  unstable.  Salts  of  the  nature  of  borax 
derived  from  tetra  boric  acid  are  more  stable.  On  heating  nickel  borate 
NiO-B2O3  to  300°  it  is  likely  that  nickel  oxide  and  tetra  borate  form  according 
to  the  equation  2NiB2O4  =  NiB4O+NiO. 

By  treatment  with  hydrogen  for  one-half  hour  at  300°  or  even  at  340°  C., 
nickel  suboxide,  not  metallic  nickel  is  stated  to  be  formed.  While  pure  nickel 
oxide  is  readily  reduced  to  the  metallic  state  by  hydrogen  at  300°  C.,  this  is 
held  not  to  occur  in  the  presence  of  boric  acid,  which  acts  to  retard  reduction. 
This  acid  belongs  to  a  class  of  bodies  which  so  hold  back  the  reducing  reaction 
that  either  resort  must  be  had  to  higher  temperatures  to  secure  the  metal,  or 
the  intermediate  suboxide  phase  obtains  according  to  circumstances. 

Summary.  1.  Neither  hydrated  nor  anhydrous  nickel  borate  has  proven 
active  as  a  fat-hardening  catalyst  at  a  temperature  of  175°  C. 

2.  By  heating  nickel  borate  in  hydrogen  at  300°  to  340°  C.,  a  partial  reduc- 
tion to  the  suboxide  of  the  nickel  oxide  present  in  the  borate,  occurs.     Due  to 
the  presence  of  the  suboxide,  the  material  subdivides  in  fatty  oils  and  acts  cata- 
lytically  at  175°  although  less  effectively  than  pure  nickel  suboxide. 

3.  If  a  fatty  oil  is  heated  with  green  nickel  borate  to  260°  C.,  and  treated 
with  hydrogen,   decomposition  occurs  with  formation  of  nickel  oxide  and  sub- 
oxide  and  these  products  act  as  hydrogen  carriers  in  the  same  manner  as  the 
decomposition  products  of  organic  nickel  salts  such  as  nickel  acetate  have  been 
observed  to  function.*     It  is  claimed  by  Erdmann  and  Rack  that  Schoenfeld  is  in 
error  in  ascribing  the  hydrogenation  of  fats  when  using  nickel  formate,  acetate, 

*  Journ.  prakt  Chem.  (N.  F.),  87,  449,  and  452. 


THE  BASE  METALS  AS  CATALYZERS  183 

etc.,  to  the  agency  of  metallic  nickel,  as  nickel  oxides  are  considered  responsible 
for  the  reaction. 

4.  No  advantages  over  nickel  oxide  have  been  found  in  nickel  borate.  The 
low  temperature  of  hardening  observed  with  the  latter  is  merely  a  consequence 
of  the  prior  formation  of  nickel  suboxide.  The  property  of  the  latter  to  act  r,s  a 
hydrogen  carrier  at  a  temperature  below  200°  C.,  was  already  known.  The 
advantages  ascribed  to  nickel  borate  by  Schoenfeld,  namely,  that  no  hydrogen 
pressure  above  atmospheric  is  required  hence  the  hydrogenation  process  may  be 
carried  out  in  very  simple  apparatus,  the  slight  degree  of  sensibility  to  catalyzer 
poisons,  the  ease  of  separation  of  the  hardened  product  from  the  catalyzer,  the 
ability  to  use  the  catalyzer  repeatedly,  are  all  features  of  value  applicable  to  the 
nickel  oxide  process  as  pointed  out  in  German  Patent  No.  266,438  and  elsewhere. 
Nickel  borate  possesses  the  practical  disadvantage  that  it  affords  nickel  oxide 
loaded  with  material  of  no  value  in  the  hardening  process. 

Nickel  Borate.  Normann  *  refers  to  hydrogenation  by  means  of  organic  nickel 
salts  such  as  the  formate,  acetate,  stearate  and  oleate  as  only  a  special  case  of 
usage  of  metallic  nickel  as  a  catalyzer  as  formation  of  the  metal  always  occurs 
before  hardening  takes  place,  f  In  fact  the  liberation  of  organic  acids  in  a  state 
of  purity  is  secured  in  many  cases  by  passing  hydrogen  into  the  corresponding 
salt  of  nickel  J  affording  a  technical  process  for  the  preparation  of  pure  concen- 
trated organic  acids.  It  also  is  known  that  inorganic  salts  of  nickel  can  be 
reduced  by  hydrogen  to  the  metallic  state  §  and  that  catalyzers  have  been  pre- 
pared by  the  reduction  of  inorganic  nickel  salts.  || 

It  is  to  be  expected  that  nickel  borate  would  be  broken  down  to  a  greater 
or  less  degree  into  metallic  nickel  and  free  boric  acid  on  heating  in  a  stream 
of  hydrogen.  This  decomposition  actually  occurs,  but  when  reduction  takes 
place  below  300°  but  very  little  boron  .trioxide  volatilizes. 

On  heating  nickel  borate  in  an  electric  furnace  at  300°  in  a  current  of  air, 
some  boric  acid  sublimes  and  the  borate  turns  to  a  deeper  shade  of  green. 
Water  hydrolyzes  the  borate,  forming  free  boric  acid  and  nickel  hydroxide. 

Nickel  borate  was  heated  in  a  current  of  hydrogen  for  one-half  to  three- 
quarters  of  an  hour  at  temperatures  ranging  from  300°  to  400°  C.  The  product 
reduced  at  300°  was  used  to  hydrogenate  cottonseed  oil  and  in  three  hours  treat- 
ment at  170°  to  180°  C.  the  iodine  number  was  reduced  from  108  to  104.5. 

By  reduction  of  the  borate  at  350°  an  iodine  number  of  101.4  was  obtained 
under  otherwise  similar  conditions.  The  borate  reduced  at  400°  was  consider- 
ably darker  in  color,  and  cotton  oil  treated  with  it  exhibited  an  iodine  number  of 
47.7.  No  hydrogenation  of  the  oil  was  perceptible  when  using  nickel  borate 
without  previous  reduction. 

In  order  to  show  the  presence  of  free  metallic  nickel  in  this  borate  catalyzer 
the  carbon  monoxide  method  If  was  applied.  It  was  found  that  free  boric  acid 
prevented  the  reaction  between  carbon  monoxide  and  nickel.  Accordingly  the 
reduced  and  cooled  borate  was  introduced  into  water  (in  an  atmosphere  of  car- 
bon dioxide  to  prevent  contact  with  oxygen),  the  mixture  warmed  on  the  water- 

*Seifen.  Ztg.,   1915,  46-47. 

fMeigen  and  Bartels,  Journ.  prakt.  Chem.,  1914,  89,  290. 

J  German  Patent  No.   217,846. 

§Gmelin -Kraut  V,  1,  23,  1909. 

||  Journ.  of  Gas  Light,  1,  7,  13,  page  31. 

IT  Chem.  Ztg.,  1915,  No.  6  and  No.  7/8. 


184  THE  HYDROGENATION  OF  OILS 

bath  and  filtered  in  such  a  manner  as  to  avoid  contact  with  air.  The  precip- 
itate, thus  freed  of  boric  acid,  was  dried  in  hydrogen  below  100°  C.,  and  after 
drying  was  exposed  to  carbon  monoxide.  The  gaseous  products  of  reaction  were 
passed  through  a  heated  tube  of  glass  and  the  rate  of  formation  of  a  nickel 
mirror  noted.  The  borate  reduced  at  300°  and  350°  quickly  yielded  a  slight 
but  distinct  nickel  mirror  while  the  product  reduced  at  400°  formed  a  heavy 
mirror.  This  is  considered  proof  Of  the  presence  of  metallic  nickel  in  the  reduced 
borate  and  the  former  only  is  responsible  for  hydrogenation.* 

Erdman  and  Rack  f  believe  the  fact  is  fully  established  that  nickel 
sub-oxide  is  formed  when  nickel  borate  is  heated  in  oil  at  260°  C., 
and  hydrogen  passed  through  the  vehicle,  also  that  the  same  product 
is  obtained  by  reducing  the  borate  as  a  dry  powder  at  340°  C.,  with 
hydrogen  gas. 

Erdmann  states  he  does  not  know  whether  or  not  metallic  nickel  is  formed 
at  400°  C.,  as  he  has  made  no  observations  at  so  high  a  temperature,  but  that 
it  is  probable  the  increase  in  temperature  has,  in  this  case,  the  same  influence  on 
the  progress  of  reduction  as  has  been  noted  with  organic  salts  of  nickel.  Bed- 
ford and  Erdmann  J  found  nickel  oxide  to  be  formed  when  such  organic  salts 
were  heated  in  oil  through  which  a  stream  of  hydrogen  was  passed,  and  only 
under  special  conditions  such  as  a  substantial  increase  in  the  temperature  was 
metallic  nickel  produced.  Erdmann  also  observes  that  Normann  refers  to 
Meigen  and  Bartels  as  confirming  the  view  that  hydrogenation  with  organic 
nickel  salts  is  only  a  special  case  of  operation  with  metallic  nickel,  although 
Meigen  and  Bartels  are  stated  not  to  have  published  anything  touching  on  this 
point.  Erdmann  reiterates  that  this  view  is  wholly  erroneous.  He  questions  the 
credibility  of  Meigen  and  Bartels'  results  in  other  respects. 

Also  it  is  asserted  by  Erdmann  that  he  was  aware  phosphomolybdic  acid 
was  not  a  reagent  suitable  to  distinguish  nickel  from  its  suboxide  as  both  bodies 
react  to  form  molybdenum  blue,  but  that  this  reagent  was  employed  on  the 
nickel  borate  to  show  that  reduction  had  taken  place.  On  the  other  hand, 
Erdmann  regards  as  positive  proof  of  formation  of  nickel  suboxides:  (1)  the 
black  color  resulting  from  subdivision  of  the  catalyzer  during  its  formation  in 
oil  and  (2)  the  lack  of  electrical  conductivity  of  the  used  and  fat-free  catalytic 
agent.  The  conductivity  also  increases  with  increase  in  temperature.  § 

Schoenfeld  ||  discusses  the  observations  of  Bosshard  and  Fischli  If 
who,  Schoenfeld  notes,  on  the  basis  of  an  experiment  with  oleic  acid, 
have  stated  that  in  the  hydrogenation  of  oils  in  presence  of  nickel 
borate,  catalytic  action  comes  into  play  only  after  the  borate  is 
decomposed. 

*  See  also  Normann  and  Schick,  Arch.  Pharm.,  252,  208-210,  1914. 
fSeifen.  Ztg.,   1915,  75. 
JJourn.  prakt.  Chem.  (2)  87,  449. 
§SeifenZtg.  1915,288. 

II  Z.  angew.  Chem.  1916,  29,  39;  J.  S.  C.  I.,  1916,  367;  J.  Chem.  Soc.  no,  1,  248. 
f  J.  S.C.I.,  1915,  1079. 


THE  BASE  METALS  AS  CATALYZERS  185 

Schoenfeld  points  out  that  his  conclusions  in  regard  to  the  favorable  action  of 
nickel  borate  as  catalyst  referred  only  to  neutral  fats  and  that  he  was  aware  of 
the  decomposition  of  nickel  borate  by  free  fatty  acids.  In  Bosshard  and  Fischli's 
experiment,  the  activity  diminished  with  increasing  decomposition  of  the  catalyst, 
and  this  confirms  Schoenf eld's  contention  that  nickel  borate  is  a  more  effective 
hydrogen  carrier  than  the  mixture  of  nickel  and  nickel  oxide  (with  boric  acid) 
formed  by  its  decomposition.  In  many  cases  hardened  fats  (especially  from 
marine  animal  oils)  produced  with  the  aid  of  nickel  or  nickel  oxide  contain  more 
nickel  than  those  prepared  with  the  aid  of  nickel  borate.  Schoenfeld  disputes 
the  statement  of  Bosshard  and  Fischli  that  the  catalytic  hydrogenation  of  oils 
in  presence  of  nickel  borate  is  conditioned  by  the  previous  decomposition  of 
the  salt;  the  reverse,  in  fact,  he  claims  is  the  case,  for  with  increasing  decom- 
position of  the  borate  owing  to  the  action  of  the  free  oleic  acid  used  in  Boss- 
hard's  experiment,  the  activity  of  the  catalyst  diminishes.  The  relatively  high 
nickel  content  of  the  oleic  acid  hardened  in  presence  of  nickel  borate  is  likewise 
to  be  attributed  by  Schoenfeld  to  the  decomposition  of  the  salt  by  the  free  fatty 
acid. 

C.  and  G.  Muller  Speisefettfabrik  A.-G.*  employ  a  hydrogena- 
tion catalyzer  consisting  of  a  nickel  salt  of  an  inorganic  acid  not 
volatile  at  the  temperature  of  hydrogenation  (e.g.,  nickel  borate  or 
silicate).  The  nickel  salts  are  preferably  heated  in  a  current  of 
hydrogen  before  use. 

The  action  of  nickel  borate  as  a  catalyzer  has  been  determined  in  the  author's 
laboratory.  A  nickel  compound  was  prepared  by  treating  a  solution  of  nickel 
sulphate  with  sodium  metaborate.  The  voluminous  precipitate  which  formed 
was  dried  in  the  air  at  100.  C.  and  subsequently  dehydrated  at  a  higher  tem- 
perature in  a  current  of  hydrogen.  This  product  hardened  cottonseed  oil  at 
about  the  same  rate  as  the  catalytic  material  used  by  Schoenfeld. 

A  catalyzer  described  by  Bremen  Besigheimer  Oelfabriken  f  is 
produced  by  calcining  organic  metal  compounds,  or  a  mixture  of 
metal  compounds  with  carbon  or  carbon-containing  substances,  and 
introducing  the  mixture,  immediately  after  calcining,  into  oil  or 
other  indifferent  liquid  in  which  it  can  be  kept  indefinitely. 

It  is  essential  that  the  calcining  should  be  continued  until  the  mixture  has 
become  pyrophorous;  as  this  quality  is  stated  to  greatly  increase  the  catalytic 
action  of  the  material. 

The  observation  is  made  that  it  has  been  previously  proposed  to  heat  or 
burn  organic  metal  compounds  or  mixtures  of  metal  compounds  and  carbon  to 
produce  finely-divided  catalytic  materials,  but  that  it  has  never  been  proposed 
to  introduce  the  materials  so  produced  directly  into  oil,  immediately  the  desired 
stage  of  the  calcining  has  been  reached;  also  that  catalysts  produced  by  reduc- 

*  French  Patent  No.   470,364,    March  28,    1914;    J.   S.   C.   I.,    1915,   186;    Swedish 
Patent  No.  41,331,  September  13,  1916;    Chem.  Abs.,  1916,  3172. 
t  British  Patent  No.  4023,  1915. 


186  THE  HYDROGENATION  OF  OILS 

tion  in  a  current  of  hydrogen  have  previously  been  rubbed  up  with  oil  to  form  a 
viscid  "  emulsion-like  fluid,"  and  the  suggestion  has  been  advanced  to  mix  a 
metal  compound  with  oil  or  other  protective  substance  and  reduce  the  mixture 
in  the  presence  of  hydrogen.  In  the  present  case,  however,  it  is  noted  that  the 
expensive,  lengthy  and  dangerous  reduction  with  hydrogen  is  entirely  avoided. 

Fats  hydrogenated  with  the  ordinary  catalyzer,  are  stated  to  have  a  peculiar 
smell  which  is  designated  as  "  catalyzer  smell."  To  eliminate  this  smell,  the 
fats  have  to  be  steamed  after  hydrogenation.  This  steaming  usually  is  regarded 
as  unnecessary  when  catalyzers  prepared  by  calcination  are  used.  The  carbon 
is  claimed  to  remove  the  typical  catalyzer  smell,  so  that  when  hydrogenating 
with  the  aid  of  these  catalyzers,  substances  are  obtained  that  can  be  used  at 
once  for  technical  purposes.  Owing  to  the  presence  of  carbon,  the  fat  is  found 
to  be  more  easily  filtered  and  at  the  same  time  bleached,  as  pyrophorous  carbon 
has  bleaching  properties. 

The  process  may  be  carried  out  in  the  following  manner: 

Benzoate  of  nickel  is  heated  above  1000°  C.  until  carbonized,  and  the  carbon 
has  completely  or  partly  reduced  the  oxide  of  nickel  formed.  The  so-called 
mixture  of  carbon  and  metal  is  then  at  once  mixed  with  oil,  or  other  indifferent 
liquid.  The  calcination  reaction  is  found  to  reach  completeness  in  a  few  min- 
utes, or  at  the  outside  in  half  an  hour. 

In  a  second  way  of  carrying  out  the  process,  carbonate  or  oxide  of  nickel, 
precipitated  on  fossil  meal,  is  mixed  with  about  the  same  quantity  of  fine  car- 
bon, and  heated  above  1000°  C.  until  the  mass  has  become  pyrophorous.  It  is 
then  introduced  without  delay  into  oil  and  is  thoroughly  mixed  with  the  latter. 
This  catalyzer  may  then  be  mixed  with  a  further  quantity  of  oil.  Its  lasting 
qualities  are  very  good. 

Oil  hardening  with  such  catalyzers  can  be  carried  out  at  150°  to  200°  Car- 
bon, which  by  itself  becomes  pyrophorous  on  being  calcined,  such  as,  for  instance, 
animal  charcoal,  is  recommended.  This  is  regarded  as  apparently  due  to  the 
fact  that  pyrophorous  carbon  alone  has  a  catalyzing  action,  and  also  assists  the 
metal  catalyzer  in  its  catalytic  action. 

The  application  of  nickel  boride  *  and  of  nickel  carbide  f  or  of 
catalyzers  containing  the  latter  is  proposed  by  Ellis.  The  catalyzer 
may  be  sealed  in  paraffin  wax. 

The  preparation  of  a  catalyzer  from  inorganic  basic  compounds 
is  described  by  Ellis.  J 

One  form  of  this  catalyzer  is  prepared  by  subjecting  nickel  hydrate  to  the 
reducing  action  of  hydrogen  in  a  submersion  or  bathing  liquid  of  oil  or  glycerine. 
The  reduction  is  carried  out  at  so  low  a  temperature  that  the  catalytic  material 
is  left  in  a  relatively  voluminous  condition.  By  the  reduction  of  mixtures  of 
nickel  hydrate  and  other  metallic  hydrates  such  as  copper  hydrate,  a  composite 
metal  powder  is  obtained  which  is  particularly  active  in  the  hydrogenation  of 
some  oils.  The  composite  catalyzer  of  nickel  and  copper  has  been  found  effective 

*U.  S.  Patents  No.  1,201,226,  Oct.  10,  1916;  1,255,590,  Feb.  5,  1918;  J.  S.  C.  I., 
1918,  214  A. 

fU.  S.  Patent  No.  1,182,995,  May  16,  1916. 
JU.  S.  Patent  No.  1,156,068,  October  12,  1915. 


THE  BASE  METALS  AS  CATALYZERS  187 

in  the  hardening  of  commercial  oleic  acid.     A  method  of  preparing  nickel  hydrate 
in  a  form  suitable  for  reduction  to  yield  catalytic  nickel  is  described  by  Ellis.* 

Some  interesting  observations  have  been  made  by  Kelber  |  on 
the  catalytic  hydrogenation  of  organic  compounds  with  non-noble 
metals  at  room  temperature. 

The  catalytic  action  of  the  reduced  nickel  metals  is  stated  to  be  greatly 
increased  if  the  compounds  employed  (best  the  basic  carbonates)  are  first  de- 
posited on  a  suitable  carrier  (infusorial  earth,  Florida  clay,  the  various  com- 
mercial hydrosilicates  of  aluminum  and  magnesium,  blood  charcoal,  the  decolor- 
izing charcoal  of  the  ferrocyanide  manufacture,  linden  charcoal,  etc.).  The 
reduction  is  best  effected  in  aqueous  or  aqueous-alcoholic  solutions.  In  alcohol, 
benzol,  acetone,  ethyl  ether  and  ethyl  acetate  it  is  slower;  the  addition  of  a 
little  water,  especially  with  ethyl  ether  and  ethyl  acetate,  greatly  accelerates  it; 
in  acetic  acid  it  is  rapid  with  nickel  reduced  at  310°.  Chloroform  is  not  suit- 
able. To  get  an  approximate  comparison  of  the  catalytic  action  of  reduced 
non-noble  metals  with  that  of  colloidal  palladium,  the  detonating  gas  catalysis 
was  carried  out;  Kelber  and  Schwarz  palladium  preparation  J  was  used;  0.2  g. 
this  (=0.0344  g.  Pd)  showed  an  activity  which  at  first  was  less  than  that  of 
0.5  g.  nickel  (a)  (from  the  basic  carbonate)  reduced  on  4.5  g.  of  an  inorganic 
carrier  in  hydrogen  at  450°,  although  it  gradually  increased  as  compared  with 
the  activity  of  the  nickel  and  finally  surpassed  it.  A  nickel  prepared  at  310°  or 
450°  without  a  carrier  gave  a  negative  result.  In  the  reduction  of  0.75  g. 
cinnamic  acid  in  50  per  cent  alcohol,  however,  preparation  (a)  and  3.0  g.  nickel 
reduced  at  450°  have  about  the  same  effect  as  0.5  g.  reduced  at  310°,  while 
0.5  g.  reduced  at  450°  without  a  carrier  is  enormously  less  effective  than  prep- 
aration (a);  in  an  aqueous  alcoholic  solution  of  sodium  cinnamate  the  nickel 
reduced  at  310°  has  the  same  effect  as  an  equal  weight  of  nickel  reduced  at 
450°  on  a  carrier.  Cobalt  may  be  used  instead  of  nickel  but  the  reduction  is 
slower.  Other  substances  reduced  in  this  way  were  sodium  phenyl  propiolate, 
quinine  hydrochloride,  diphenyldiacetylene,  sodium  "  cotton  oleate."  Details 
of  the  various  experiments  showing  the  amounts  of  hydrogen  absorbed  in  dif- 
ferent time  intervals  are  given. 

Fuchs  §  observes  that  carbonates  of  some  base  metals,  such  for 
instance  as  nickel  carbonate,  can  be  converted  directly  into  metals 
in  a  very  finely-divided  condition  by  immersing  or  suspending  this 
material  in  the  fatty  acid  or  oil  to  be  reduced  and  heating  in  the 
presence  of  hydrogen  to  the  specific  reduction  temperature  for  each 
compound,  which  lies  between  210°  and  290°  C.  After  the  formation 
of  the  catalyzer  is  complete  the  temperature  is  lowered  and  the 
reduction  of  the  oil  is  effected.  By  such  procedure  the  catalyzer  is 
prevented  from  coming  into  contact  with  the  air.  In  plants  where 

*U.  S.  Patent  No.  1,166,956,  Dec.  28,  1915. 

tChem.  Abs.,  1916,  837;    Ber.  49.   1916,  55-63. 

J  Chem.  Abs.  6,  2757. 

§  Chem.  Abs.,  1914,  3636;    British  Patent  No.   11,542,   1913. 


188  THE  HYDROGENATION  OF  OILS 

hydrogenation  is  performed  with  the  circulation  of  a  hydrogen 
atmosphere  the  employment  of  organic  salts  of  metals  is  held  by 
Fuchs  to  be  impracticable  because  the  oxide  of  carbon  which  is 
constantly  generated  cannot  be  eliminated  from  such  hydrogen 
atmosphere  except  at  high  cost.  As  an  example  of  Fuchs'  method, 
castor-oil  is  mixed  with  1.2  per  cent  of  finely-powdered  and  prefer- 
ably freshly-prepared  nickel  carbonate  previously  dried  at  a  tem- 
perature of  110°  C.  and  the  mixture  is  then  heated  to  a  temperature 
of  230°  C.  while  a  current  of  hydrogen  is  allowed  to  pass  slowly 
therethrough.  As  soon  as  this  temperature  is  attained,  compressed 
hydrogen  (twelve  to  fifteen  atmospheres)  is  admitted  into  the  mix- 
ture through  a  nozzle.  The  reduction  of  the  salt  to  metallic  nickel 
takes  place  with  a  slight  frothing  due  to  the  evolution  of  water.  As 
soon  as  this  operation  is  completed  the  temperature  is  lowered  and 
the  reduction  of  the  oil  is  carried  out  as  an  uninterrupted  continua- 
tion of  the  preceding  operation. 

Catalytic  substances  such  as  metals  on  an  inert  carrier  which  have 
been  used  in  hydrogenating  oils  or  fats  are  regenerated  according  to 
Morrison's  method  *  by  expressing  most  of  the  oleaginous  material 
from  the  catalyst  so  as  to  form  the  latter  into  briquets  or  cakes, 
burning  out  residual  organic  substances  and  then  recovering  the 
metal  in  catalytically  active  form  by  heating  in  hydrogen. 

Morrison  observes  that  great  difficulty  is  experienced  in  revivifying 
metallic  catalysts,  either  wholly  metallic  or  on  an  inert  support, 
which  have  been  "  spent "  in  the  hydrogenation  of  fats  and  oils. 
The  most  direct  way  is  to  dissolve  out  the  fats,  etc.,  with  a  suitable 
solvent,  then  reduce  in  an  atmosphere  of  hydrogen.  It  has  been 
found  that  there  is  much  organic  matter  present,  which  is  not  sol- 
uble in  ordinary  solvents  and  when  it  has  been  sought  to  burn  out 
this  organic  matter  difficulties  arise.  If  a  reducing  temperature  or 
temperature  below  the  point  of  ignition  in  the  air  is  employed,  the 
material  is  apt  to  char,  leaving  a  great  deal  of  carbon  in  the  material. 
If  the  material  is  heated  in  an  oxidizing  atmosphere  and  at  a  tem- 
perature which  will  burn  out  all  the  organic  matter,  it  is  found  that 
it  is  not  catalytically  active  when  reduced  in  hydrogen.  Further 
it  is  very  difficult  to  burn  out  completely  a  light  pulverulent  mate- 
rial without  frequent  turning  over,  to  expose  the  unburned  portion 
to  the  air.  In  turning  it  over,  it  dusts  easily,  entailing  losses. 
Morrison  recommends  that  the  material  as  it  comes  from  the  filter- 
ing or  settling  apparatus,  either  after  being  extracted  -with  a  suitable 

*U.  S.  Patent  No.   1,203,233,  October  31,   1916;    Chem.  Abs.;   1917,   105. 


THE  BASE  METALS  AS  CATALYZERS  189 

solvent  or  direct,  containing  all  the  oil  and  organic  matter,  be  sub- 
jected to  pressure,  preferably  in  a  hydraulic  press,  at  about  2000  Ib. 
per  square  inch  in  order  to  extract  as  much  oil  as  possible.  Cakes 
or  briquets  are  thus  formed,  which  can  be  readily  and  completely 
burned  out,  without  the  necessity  of  turning  them  over  to  better 
expose  to  the  air,  as  the  lumps  allow  a  free  circulation  of  air.  After 
the  material  is  sufficiently  burned  (a  small  per  cent  of  carbon  does 
not  interfere),  it  is  macerated  with  water  and  sufficient  mineral 
acid  is  added  to  dissolve  all  the  metallic  portion.  This  is  done  in  a 
vessel  which  contains  a  mechanical  agitator  to  keep  the  material  in 
suspension.  When  the  metal  or  oxide  is  dissolved  and  still  while 
agitating  the  metal  salt  is  precipitated  as  a  hydrate  or  carbonate  by 
sodium  carbonate.  It  is  now  washed  practically  free  of  any  soluble 
salts  which  would  interfere  with  its  activity,  i.e.,  salts  which  would 
act  as  "  poisons "  either  before  or  after  reducing,  such  as  sodium 
sulphide  or  sodium  sulphate.  A  washing  filter  press  is  recom- 
mended for  this  purpose.  The  washed  product  is  dried,  ground  and 
reduced  in  an  atmosphere  of  hydrogen.  Morrison  states  that  it  will 
be  found  to  have  regained  its  original  activity. 

Nickel  oxides  used  as  catalytic  agents  in  the  hydrogenation  of  oils  may  be  regen- 
erated by  removing  the  grease,  calcining  with  limited  access  of  air  so  as  to  produce 
suboxide,  or  with  free  access  of  air  to  produce  monoxide,  washing  if  necessary  (e.g., 
if  a  chlorinated  solvent  has  been  used  for  extracting  grease)  and  drying.  The  mon- 
oxide thus  obtained  may  be  converted  into  suboxide  by  a  limited  dry  reduction  by 
hydrogen,  the  operation  not  being  pushed  so  far  as  to  produce  apyrophoric  product.* 

A  catalyzer  rendered  inactive  by  adhering  fat  is  treated  by  Haas,f 
in  an  autoclave,  under  pressure  to  saponify  the  fat. 

In  using  nickel  in  a  colloidal  form  difficulty  is  experienced  in  the 
filtration  of  oil  in  which  such  a  body  is  suspended  and  Ellis  t  has 
proposed  the  filtration  of  oil  containing  colloidal  nickel  through 
a  bed  or  layer  of  hydrated  silicic  acid  or  silicate  such  as  zeolite  or 
natural  silicate  containing  hydrous  material. 

In  carrying  out  this  process  the  bulk  of  the  catalytic  material  may  be  removed 
by  coarse  filtration.  The  oil  carrying  the  finer  particles  of  the  catalyzer  is 
passed  through  a  filter  containing  the  hydrated  silicic  acid  or  hydrated  silicate. 
An  ordinary  filter  press  may  be  used  for  this  purpose  and  the  silicious  material 
may  be  applied  to  the  filter  cloths  by  passing  through  the  press  a  quantity  of 
hardened  oil  in  a  molten  condition  containing  the  silicious  material,  thereby 

*Soc.  Industrielle  de  Products  Chimigues.  British  Patent  No.  112,768,  Nov.  5f  1917; 
Chem.  Abs.,  1918,  1258. 

t  Norwegian  Patent  No.  28,034,  July  2,  1917;    Chem.  Abs.,  12,  98. 
JU.  S.  Patent  No.   1,224,291,   May  1,   1917. 


190  THE  HYDROGENATION  OF  OILS 

forming  a  silicious   coating  on   the   filter   cloths.     An  effective   form   of  filtering 
agent  is  prepared  by  precipitating  silicic  acid  on  kieselguhr  or  fuller's  earth. 

Bosch,  Mittasch  and  Schneider  *  suggest  a  form  of  catalytic  mate- 
rial useful  for  carrying  out  hydrogenation  and  dehydrogenation 
rapidly,  with  certainty  and  at  comparatively  low  temperatures. 
An  intimate  mixture  of  a  common  metal,  iron,  nickel,  cobalt  and 
copper,  with  a  phosphate  of  an  alkaline  earth  metal  as  a  promoter, 
is  employed.  It  is  necessary  to  effect  an  intimate  mixture  of  the 
catalytic  metal  and  the  promoter.  If  calcium  phosphate  be  em- 
ployed as  the  promoter,  the  oxide  or  carbonate  of  the  catalytic 
metal  can  be  mixed  with  calcium  phosphate  and  the  mixture  there- 
upon be  heated  and  reduced.  A  still  better  method  consists  in 
taking  an  insoluble  salt,  such  as  the  carbonate,  or  an  oxide  of  the 
catalytic  metal,  and  adding  to  it  a  solution  of  a  calcium  salt,  for 
instance,  calcium  nitrate,  and  then  to  add  the  necessary  quantity  of 
phosphoric  acid  either  as  such  or  in  the  form  of  ammonium  phos- 
phate, or  alkali  metal  phosphate,  in  order  to  convert  the  calcium  into 
phosphate.  It  is  preferred  to  employ  basic  phosphates,  such  as  tri- 
calcium  phosphate,  as  promoters. 

It  is  advantageous  for  the  purpose  of  making  a  very  active  con- 
tact mass  to  prepare  the  catalytic  metal  from  carbonaceous  salts  or 
mixtures  of  such  salts,  for  instance,  from  carbonates  or  from  for- 
mates. It  is  often  useful  to  add  to  the  mixture,  bodies  of  inorganic 
or  organic  nature,  which  act  either  as  carriers,  or  as  binding  agents, 
or  which  increase  the  porosity  of  the  contact  mass.  Asbestos,  char- 
coal, or  pumice  may  be  used.  The  catalytic  metal  can  be  employed 
either  in  a  state  of  fine  division,  or  in  a  more  compact  form,  such  as 
wire  netting,  or  wool,  or  in  sheet  form. 

Catalytic  mixtures  made  according  to  this  method  can  be  used 
for  the  hydrogenation  and  dehydrogenation  of  compounds  containing 
carbon  and  are  of  particular  value  for  the  hardening  of  fats  and 
fatty  acids. 

The  reaction  can  be  carried  out  either  at  ordinary  pressure,  or 
under  increased  pressure,  for  instance,  above  fifty  atmospheres  and  in 
most  cases  proceeds  sufficiently  rapidly  at  temperatures  1  elow  180°  C. 

Example:  Suspend  5  parts  by  weight  of  nickel  carbonate  in  a 
solution  of  1.3  parts  of  calcium  nitrate,  and  then  precipitate  the  cal- 
cium by  the  addition  of  0.7  part  of  ammonium  phosphate 
(NH4H2P04).  Filter,  wash  well,  dry  and  reduce  with  hydrogen  at 

*U.  S.  Patent  No.  1,215,335,  February  13,  1917.  See  also  No.  1,271,013,  July  2, 
1918. 


THE  BASE  METALS  AS  CATALYZERS  191 

about  350°  C.  This  contact  mass  may  be  employed  in  the  reduc- 
tion of  cottonseed  oil  by  means,  of  hydrogen  at  about  130°  C.  In 
another  case  *  the  same  investigators  employ  an  oxide  of  boron  as  a 
promoter  and  as  an  example  they  recommend  to  mix  freshly-pre- 
cipitated nickel  carbonate  with  10  per  cent  of  its  weight  of  ammo- 
nium borate  previously  dissolved  in  water.  The  product  is  dried 
and  reduced.  Calcium  borate  may  be  similarly  used.  This  cata- 
lyzer is  recommended  for  hardening  fish  oil. 

ORGANIC  SALTS  OF  NICKEL  AS  RAW  MATERIALS  FOR  CATALYZERS, 
METALLIC  FORMATES  AND  OLEATES 

Snelling  f  observes  that  in  the  use  of  a  siliceous  carrier  with  an 
oxide  it  is  difficult  to  prevent  more  or  less  formation  of  slaggy  com- 
pounds, but  that  a  catalyzer  of  high  reactivity  can  be  prepared  by 
heating  the  metallic  formates,  the  reduction  of  which  takes  place  at 
a  very  low  temperature,  and  proceeds  smoothly. 

Nickel,  cobalt,  iron  and  copper  formate,  etc.,  may  be  used;  and  these  salts 
may  be  employed  in  the  dry  state  where  a  powder  is  required;  or  a  porous 
carrier  may  be  soaked  with  a  solution  of  the  formate,  dried  and  reduced.  On 
heating,  the  formates  decompose  with  an  evolution  of  carbon  monoxide  and 
hydrogen,  both  strongly  reducing  gases;  and  this  evolution  of  these  gases  in 
statu  nascendi,  allows  the  formation  of  highly  reactive  metal  at  very  low  tem- 
peratures. It  is  not  necessary  as  in  the  case  of  nitrates,  to  supply  the  reducing 
means  from  another  source;  which  is  regarded  by  Snelling  as  an  advantage  in 
the  case  of  forming  the  catalyst  on  a  support.  In  the  formates,  the  combus- 
tible and  the  oxygen  of  the  metal  oxide  are  in  atomic  or  molecular  contact;  a 
contact  differing  from  that  of  the  oxide  as  powder  in  an  atmosphere  of  hydrogen. 
And,  as  the  reduction  of  the  metal  oxide  and  the  oxidation  of  the  combustible 
as  a  total  reaction  is  exothermic,  a  reduction  change  started  in  one  portion  of  a 
mass  of  formate  tends  to  spread  through  it;  the  reaction  it  is  stated  can  be 
initiated  at  one  point  and  allowed  to  spread  through  the  material  as  a  self- 
propagating  reaction.  The  reduction  may  be  effected  at  a  comparatively  very 
low  temperature;  a  temperature  at  which  there  is  no  tendency  of  the  reduced 
metal  to  sinter  or  of  the  oxides  to  slag. 

In  making  reactive  copper  where  the  metal  is  desired  in  pulverulent  form, 
copper  formate  is  first  dried  at  a  low  temperature  and  is  then  cautiously  heated 
in  a  container  to  the  lowest  temperature  at  which  the  formation  of  metal  becomes 
evident.  The  air  in  the  tube  is  best  displaced  by  hydrogen  prior  to  heating. 
The  formate  may  be  dried  in  the  container  in  which  reduction  is  subsequently 
to  be  effected.  In  so  doing  it  is  advantageous  to  pass  through  a  stream  of 
hydrogen  or  other  non-oxidizing  gas.  This  stream  carries  away  as  fast  as  formed 
the  water  produced  in  drying  and  that  produced  in  the  subsequent  reduction  and 
much  facilitates  both  operations.  A  vacuum  may  be  used  in  lieu  of  hydrogen. 

*U.  S.  Patent  No.  1,215,334,  February  13,  1917. 

fU.  S.  Patent  No.  1,122,811,  December  29,  1914;    J.  S.  C.  I.,  1915,  182. 


192  THE  HYDROGENATION  OF  OILS 

Where  the  copper  is  carried  on  a  support,  the  carrier  may  be  soaked  in  a  solution 
of  copper  formate  and  the  impregnated  material  dried  and  heated  in  the  same 
way.  It  is  particularly  advantageous  in  this  case  after  placing  the  impregnated 
carrier  in  the  reduction  vessel  to  produce  a  vacuum  to  remove  adsorbed  air. 
Hydrogen  is  then  allowed  to  enter  and  the  material  heated. 

The  porous  carrier  employed  may  be  any  of  the  usual  refractory  materials. 
For  nickel,  cobalt,  iron,  copper,  etc.,  where  used  for  hydrogen  addition,  as  in 
hardening  fats,  the  carrier  may  be  coke.  Where  used  in  oxidizing  reactions,  as 
in  the  manufacture  of  formaldehyde,  the  carrier  is  better  an  inoxidizable  material 
such  as  pumice-stone,  baked  clay,  kieselguhr,  etc.  For  many  purposes  Snelling 
finds  that  alundum  is  a  desirable  carrier  since  in  some  reactions  alumina  has  a 
catalytic  action.  It  is  particularly  advantageous  in  making  a  copper  catalyst 
for  the  manufacture  of  formaldehyde. 

For  many  purposes  in  catalytic  operations  Snelling  states  it  is  desirable  to 
have  a  column  of  catalytic  material  wherein  the  carrier  has  different  proportions 
of  catalyst  at  different  points  throughout  the  column.  For  example,  in  making 
formaldehyde  from  methyl  alcohol  and  air  it  is  advantageous  to  have  the  mixed 
vapor  and  air  pass  through  an  alundum  carrier  containing  a  relatively  small 
amount  of  copper,  then  past  a  carrier  containing  more,  and  so  on  until  the 
mixture  finally  passes  a  carrier  relatively  rich  in  catalyst.  It  is  regarded  as 
advantageous  to  have  the  concentration  of  the  reactive  bodies  inversely  pro- 
portional in  any  given  zone  of  catalysis.  Similarly  in  hydrogenation  processes 
involving  the  addition  of  hydrogen  to  vapors  and  gases,  it  is  advantageous  to 
have  the  gas  mixture  first  pass  through  a  carrier  containing  relatively  little 
reduced  nickel  and  subsequently  past  a  carrier  containing  more  nickel. 

As  stated,  the  reduction  of  the  formate  should  be  at  the  lowest  possible 
temperature;  and  the  material  should  be  brought  at  this  temperature  rather 
gradually.  Careful  observation  of  any  given  formate  will  show  to  the  eye  the 
point  where  reduction  begins.  Any  violent  heating  causes  a  sudden  decomposi- 
tion of  the  formate  with  the  liberation  of  carbon  monoxide  and  hydrogen  in  the 
gaseous  form;  after  which  reduction  can  only  be  in  the  ordinary  way;  viz.,  by 
a  reducing  atmosphere.  With  violent  heating  the  reaction,  under  the  catalytic 
influence  of  the  metal,  is  apt  to  be  irregular  and  result  in  the  production  of 
carbon  and  other  bodies. 

Spieler  *  states  he  has  found  that  gelatinous  aluminum  hydrate, 
also  gelatinous  silicon  hydrate  possess  catalytic  properties  in  a  slight 
degree,  not  sufficiently  marked  to  be  of  value  as  a  commercial 
catalyst  when  used  by  themselves;  however,  when  in  contact  or  in 
combination  with  nickel  salts  the  catalytic  properties  of  these  hy- 
drates are  remarkably  increased,  so  much  that  such  a  compound 
or  combination  has  far  greater  catalytic  activities  than  either  of  the 
component  ingredients  themselves. 

When  a  nickel  salt  of  an  organic  acid,  such  as  nickel  formate  (also  nickel 
carbonate),  is  intimately  incorporated  with  a  preponderating  quantity  of  inor- 
ganic colloids,  such  as  gelatinous  aluminum  hydrate  or  gelatinous  silicon  hydrate, 

*U.  S.  Patent  No.  1,139,592,  May  18,  1915. 


THE  BASE  METALS  AS  CATALYZERS  193 

either  singly  or  together,  in  the  dry  state,  or  with  water  to  form  a  pasty  mass, 
and  this  heated  with  a  quantity  of  fat  or  oil  to  a  temperature  approximately 
230°  to  250°  C.  in  a.  pressure  vessel  arranged  to  agitate  the  contents,  a  catalyzer 
of  uniform  activity  and  stability  can  be  produced. 

In  preparing  this  catalytic  compound,  in  the  event  the  chemical  ingredients 
are  in  the  form  of  a  pasty  mass,  during  the  stage  of  the  evaporation  of  the 
water  and  the  subsequent  heating  to  the  final  temperature,  a  brisk  agitation  of 
the  mass  is  desirable,  as  by  this  procedure  the  entire  catalytic  substance  is 
finely  and  uniformly  distributed  throughout  the  suspension  medium. 

During  the  stage  of  evaporation  of  the  water  of  solution,  some  intermediate 
reactions  may  occur  between  the  nickel  formate  or  carbonate  and  the  inorganic 
colloids;  however,  the  final  decomposition  of  the  nickel  formate  may  be  ex- 
pressed by  the  equation 

Ni(COOH)2  =  Ni+2H+CO2, 
and  that  of  the  nickel  carbonate  as 

NiC03=NiO+C02. 

The  hydrogen  liberated  during  the  decomposition  of  the  formate  is  in  the 
nascent  state  and  within  the  oil-covered  particles  is  absorbed  by  the  catalyzer, 
which  is  then  fully  charged  with  the  hydrogen  content  it  is  capable  of  occluding. 
In  this  manner  the  catalyzer  is  preserved  in  its  most  potent  state. 

A  convenient  method  of  preparing  this  catalyzer  is  to  take  40  parts  of  nickel 
formate  and  carbonate  in  aqueous  suspension  and  thoroughly  incorporate  this 
with  about  80  parts  of  gelatinous  aluminum  hydrate  or  gelatinous  silicon  hydrate, 
either  singly  or  together,  in  any  proportion.  The  proportion  of  nickel  formate 
and  carbonate  may  be  varied  considerably.  The  proportion  may  be  as  low  as 
4  parts  of  one  to  36  parts  of  the  other  with  satisfactory  results.  This  mixture 
is  placed  in  an  agitating  vessel  with  100  parts  of  a  suspensory  medium  (oil)  and 
the  whole  mass  is  heated  with  constant  agitation.  The  steam  resulting  from 
the  evaporation  of  the  aqueous  solution  is  allowed  to  escape.  When  the  water 
has  been  driven  off,  the  temperature  is  raised  to  approximately  235°  to  250°  C. 
and  this  temperature  maintained  until  the  reaction  is  complete. 

Another  procedure  is  to  take  nickel  formate  and  carbonate,  and  air-dried 
gelatinous  aluminum  hydrate  or  silicon  hydrate,  or  both  together,  thoroughly 
incorporate  these  and  put  in  a  pressure  vessel  with  a  quantity  of  fat  or  oil, 
agitate  and  heat  the  mass  to  a  temperature  of  approximately  235°  to  250°  C. 
until  the  reaction  is  complete. 

Higgins  *  notes  that  in  order  to  prepare  a  catalytic  body  from 
fatty  acid  salts  of  nickel  and  cobalt  it  is  not  necessary  to  treat  them 
with  hydrogen  but  that  it  is  sufficient  to  mix  the  salt  with  a  fatty 
oil,  and  to  heat  the  mixture,  to  produce  a  substance  possessing  cata- 
lytic properties.  Thus  the  fatty  acid  salts  of  nickel,  cobalt,  iron  or 

*  British  Patent  Nos.  21,041  and  23,873,  1913.  J.  S.  C.  I.,  1916,  1122;  Chem.  Abs., 
1917,  219;  British  Patent  No.  29,  Sept.  17,  1913;  Chem.  Abs.,  1917,  105;  see  also  Brit- 
ish Patent  No.  4,144  of  1913;  Holland  Patent  No.  2,322,  Feb.  15,  1918  to  Wimmer  and 
Higgins. 


194  THE   HYDROGENATION   OF  OILS 

copper  may  be  heated  in  a  protective  neutral  or  inert  medium  such 
as  a  fatty  body  or  oil. 

The  reaction  may  be  carried  out  by  merely  mixing  the  organic  metal  salt  with 
the  medium  or  fatty  body  and  while  heating  the  mass,  submitting  it  to  sufficient 
mechanical  mixing  to  maintain  it  at  a  uniform  temperature  throughout.  With 
such  treatment  the  mass  blackens  and  the  degree  of  this  blackening  may  be 
taken  as  a  guide  as  to  the  extent  to  which  the  catalytic  body  is  produced.  The 
temperatures  required  will  be  determined  accordingly,  being  varied  according  to 
the  salt  used,  the  lowest  temperature  at  which  treatment  can  be  conveniently 
carried  out  being  best.  As  the  temperatures  are  relatively  high  (from  200°  to 
260°  C.)  it  is  recommended  to  perform  the  reaction  in  a  vessel  from  which  air  is 
excluded  thus  preventing  undesirable  oxidation  of  the  fatty  body.  By  passing 
through  the  mixture  a  stream  of  indifferent  gas,  such  as  carbon  dioxide  or  nitrogen, 
contact  with  air  is  avoided.  Mechanical  stirring  may  be  employed  in  such  cases 
but  if  the  stream  of  indifferent  gas  be  sufficiently  rapid  this  is  not  necessary. 

In  heating  the  reaction  mass,  it  is  desirable  to  use  an  oil  bath,  as  the  devel- 
opment of  local  superheating  may  produce  side  reactions,  tending  to  diminish 
the  activity  of  the  catalytic  mass.  * 

On  passing  hydrogen  through  nickel  formate  and  gelatin  in  glycerine,  at  200 
to  210°  C,  colloidal  nickel  is  obtained.* 

A  volatile  organic  acid  of  the  nature  of  formic  acid  has  been 
found  by  Higgins  f  to  accelerate  catalysis.  The  formic  acid  may 
be  used  as  a  liquid  or  in  the  state  of  vapor.  It  may  be  sprayed 
into  the  substance  to  be  treated  or  into  the  vessel  in  which  the 
process  is  conducted  or  carried  into  the  reaction  mass  in  vapor 
form  in  the  hydrogen  employed,  the  object  in  each  case  being  to 
insure  that  catalysis  may  take  place  in  the  presence  of  the  free  vola- 
tile organic  acid.  By  the  action  of  formates  and  similar  compounds 
reduction  is  effected,  without  heating  under  pressure.  For  example, 
cottonseed  oil  may  be  reduced  by  heating  at  210°  C.  with  60  per  cent 
of  its  weight  of  nickel  formate,  air  being  excluded.  J 

The  oxalates,  tartrates  and  acetates  of  nickel  and  iron  are  men- 
tioned as  catalyzer  raw  materials  in  the  preparation  of  a  catalytic 
body  used  by  Valpy  and  Lucas  §  in  the  cracking  of  hydrocarbon  oils. 

Finely-divided  copper  prepared  by  reduction  of  copper  salts,  such 
as  the  nitrate  or  carbonate  or  organic  salts  which,  on  heating, 
evolve  indifferent  gases,  e.g.,  copper  formate  or  oxalate,  is  used  for 
the  reduction  of  nitro  compounds.  These  salts  may  be  heated  alone 
or  with  ammonium  carbonate  and  when  necessary,  a  reducing  gas — • 

*Kelber,  J.  Ind.  Eng.  Chem.,  1918,  396. 
t  U.  S.  Patent  No.  1,211,704,  January  9,  1917. 

J  British  Patent  No.  4,665,  Feb.  23,  1914;  J.  S.  C.  I.,  1916,  317;  see  also  British  Patent 
No.  23,377,  of  1912;  J.  S.  C.  I.,  1913,  989. 
§  British  Patent  No.  5847,  March  7,  1914. 


THE  BASE   METALS  AS  CATALYZERS  195 

hydrogen  or  carbon  monoxide — is  passed  over  the  catalyzer  raw 
material  at  a  temperature  below  red  heat  to  form  the  metal.  The 
copper  may  be  supported  on  a  pumice,  asbestos,  kieselguhr  or  other 
carrier. 

Activators  for  the  copper  catalyst  are  recommended.  Alkali 
compounds,  magnesia  and  alumina  are  effective.  When  employing 
copper  formate,  no  treatment  with  a  reducing  gas  is  necessary. 
Reduction  is  best  carried  out  at  about  300°  C.  In  some  cases  copper 
oxide  is  formed  as  an  intermediate  compound.  An  excessive  tem- 
perature gives  a  catalyzer  which  deteriorates  too  rapidly  in  use. 

This  form  of  catalyzer  affords  good  results  in  the  reduction  of 
aromatic  nitro  compounds  at  temperatures  around  200°  C.  yielding 
the  corresponding  amines  in  a  satisfactory  state  of  purity.  The 
contact  material  remains  active  indefinitely.* 

Richardson  f  aims  to  prepare  active  catalytic  metal,  or  compounds, 
at  a  comparatively  low  temperature  and  in  a  colloidal  condition  or 
in  a  fine  state  of  suspension  approaching  the  colloidal  condition,  in 
oils  or  fats. 

In  order  to  bring  about  this  result  he  uses  a  salt  or  compound  of  the  desired 
metal,  which  may  be  copper,  cobalt,  nickel,  or  iron,  selecting  a  salt  which  is 
soluble  in  oil  or  fat,  and  dissolves  it  in  the  oil  or  fat,  using  heat  if  necessary. 
In  order  to  reduce  the  active  metal  from  the  solution  so  obtained,  a  reducing 
substance  such  as  hydrogen  is  applied  and  reduction  in  the  cold  or  by  means 
of  heat  and  under  ordinary  atmospheric  pressure  or  higher  pressures,  is  brought 
about.  As  suitable  oil-soluble  metallic  salts  for  the  purpose,  the  metallic  salts 
of  the  fatty  acids,  are  recommended. 

The  fat  or  oil  in  which  the  reduction  with  production  of  active  catalyst  is 
to  be  brought  about  is  placed  in  a  suitable  vessel  and  to  it  is  added  from  1 
to  50  per  cent  of  a  metallic  soap  or  a  metallic  salt  of  one  of  the  higher  fatty 
acids,  for  example,  nickel  oleate,  which  is  dissolved  by  means  of  heat.  A  suit- 
able reducing  agent,  which  may  be  hydrogen,  under  pressure  or  not,  is  intro- 
duced and  solution  and  reducing  agent  are  thoroughly  intermixed  by  agitation. 
At  the  end  of  the  operation,  the  nickel  or  other  metal  is  obtained  in  a  colloidal 
highly  active  condition  or  in  a  state  of  extremely  fine  subdivision  approaching 
the  colloidal  condition,  and  can  then  be  used  to  bring  about  many  chemical 
reactions  such  as  the  addition  of  hydrogen  to  unsaturated  fatty  acids  and  fats. 
In  or  after  reducing  the  nickel  soap  with  hydrogen,  the  hydrogen  also  tends  to 
saturate  the  oil. 

According  to  Hausamann  |  the  effective  hydrogenation  of  urisat- 
urated  substances  is  obtained  by  the  use  of  a  basic  compound  of  a 
suitable  metal  (for  example,  copper,  nickel,  cobalt,  and  other  non- 

*  Zeitsch.  angew.  Chem.  Referat.,  1915,  212;    German  Patent  No.  282,568. 

t  U.  S.  Patent  No.  1,151,718,  August  31,  1915. 

JU.  S.  Patent  No.   1,145,480,  July  6,   1915,  Canada,   157,396,  August  18,   1914. 


196  THE  HYDROGENATION  OF  OILS 

noble  metals),  with  a  fatty  acid  soluble  in  the  fatty  compound  to  be 
treated,  such,  for  example,  as  oleic,  stearic,  or  like  acid. 

These  metallic  soaps  dissolve  in  the  melted  fats  or  oils,  and,  on  passing  hydro- 
gen through  the  mixture  (at  a  temperature  between  100°  and  180°  C.)  a  colloidal 
metallic  hydride  is  formed  that  is  regarded  as  the  active  agent  in  the  reducing  or 
hydrogenating  reaction.  The  hydride  exists  in  the  mixture  as  long  as  there  is 
free  hydrogen  present.  Small  additions  of  such  a  metallic  soap  are  sufficient 
to  reduce  large  quantities  of  the  unsaturated  materials.  The  same  fatty  acids 
as  exist  (usually  as  glycerides)  in  the  compounds  to  be  treated  are  preferably 
employed  to  form  the  basic  metallic  compound  used  for  catalysis.  The  conversion 
of  the  basic  metallic  compound  into  an  active  catalyzer,  when  dissolved  in  the 
fatty  material,  takes  place  gradually  in  the  hydrogen  atmosphere  at  temperature 
above  100°  C.  and  a  higher  temperature  of  from  160°  to  180°  C.  is  recommended 
in  practice.  At  this  temperature  copper  or  other  hydride  is  obtained  in  colloidal 
condition. 

As  an  example  of  the  process  the  following  may  be  taken:  500  parts  by  weight 
of  raw  soya-bean  oil  are  mixed  with  0.4  per  cent  of  the  basic  oleate  of  nickel: 

Ni(OH)C.8H2302, 

and  the  mixture  is  exposed  at  about  160°  C.  to  the  action  of  hydrogen  by  any 
of  the  well-known  methods  until  the  desired  degree  of  hardening  is  attained. 
In  using  a  basic  oleate  of  copper 

Cu(OH)C18H3302, 

dissolved  in  the  fat  and  uniformly  distributed  throughout  the  whole  mass,  the 
compound  is  acted  upon  by  hydrogen  with  the  formation  of  water  and  the  mass 
becomes  dark  brown.  At  this  stage  the  freed  hydroxyl  group  probably  plays  a 
part  in  the  formation  of  a  copper  hydride.  By  alternate  formation  and  decom- 
position of  this  colloidal  copper  hydride  the  hydrogen  is  rendered  active,  con- 
verting the  unsaturated  fatty  compounds  into  saturated,  for  instance  the  oleic 
acid  into  stearic  acid.  Analogous  reactions  occur  with  the  various  metallic  com- 
pounds which  may  be  employed  in  accordance  with  this  invention.  In  no  case  is 
the  metal  itself  produced  or  its  oxide,  as  in  some  of  the  prior  processes,  except 
at  the  end  of  the  reaction,  when  free  hydrogen  is  eliminated  to  gradually  decom- 
pose the  hydride. 

The  reactions  which  occur  may  be  given  approximately  by  the  following  equa- 
tions: 

Formation  of  the  primary  catalyst 
Cu(OH)2+CH3— 7(CH2)— CH=CH— 7(CH2)—  COOH 

=CH3— 7(CH2)— CH=CH— 7(CH2)— COO-CuOH+HzOi. 

that  is,  basic  copper  oleate. 

The  reaction  of  this  oleate  with  hydrogen 
2(CH3— 7(CH2)— CH=CH— 7(CH2)— COO  •  CuOH)  +HX 

=  2(CH3— 7(CH2)— CH=CH— 7(CH2)—  COOH)+Cu2H2+Hx_fl 
+2H2O-  -»  CH3— 7(CH2)— CH— CH— 7(CH2)— COOH+2H2O+Hx-<j. 

I        / 
Cu2H2 


THE  BASE  METALS  AS  CATALYZERS  197 

The  resulting  products  are 

CH3— 7(CH2)— CH2— CH2— 7(CH2)— COOH+Cu2H2+2H2O+Hx_8. 

A  process  for  converting  unsaturated  fatty  acids  into  saturated 
compounds  similar  to  the  foregoing  is  described  by  Mellersch- 
Jackson  *  according  to  which  a  basic  heavy  metal  salt  of  a  fatty 
acid  of  high  molecular  weight  is  dissolved  in,  or  intimately  mixed 
with,  the  substance  to  be  treated,  and  the  material  hydrogenated 
between  100°  and  180°  C.  Basic  oleates  of  nickel  and  copper  are 

mentioned.! 

A  catalyzer  is  prepared  by  Thieme  and  Geitel  {  by  heating  a  mix- 
ture of  nickel  nitrate  and  an  organic  salt  of  nickel.  The  latter  may 
be  prepared  by  the  moderate  oxidation  of  glycerine  with  nitric  acid 
and  subsequent  neutralization  with  nickel  carbonate.  The  compounds 
of  other  metals  also  may  be  used. 

They  observe  §  that  the  property  of  "  emulsifying  "  possessed  by  this  form  of 
catalyzer  permits  the  employment  of  a  very  simple  apparatus  and  hydroge nation 
is  effected  at  low  temperatures.  (140°  to  150°.)  The  process  is  stated  to  pos- 
sess the  advantage  over  former  methods  in  that  a  metal  oxide  catalyzer  or  a 
metal  catalyzer  can  be  produced  directly,  so  that  a  reduction  of  the  catalyzer 
in  a  current  of  hydrogen  is  not  necessary.  Pure  nickel  glycerate  need  not  be 
used,  as  a  mixture  of  nickel  salts  can  be  used  which  is  obtained  by  moderate  oxi- 
dation of  glycerol  and  subsequent  neutralization  with  nickel  carbonate.  For 
example,  3  parts  of  glycerine  of  33  per  cent  strength  are  mixed  with  2.5  parts 
of  62  per  cent  nitric  acid.  Some  potassium  nitrite  solution  is  added  as  cata- 
lyzer. The  mixture  is  allowed  to  stand  for  three  to  four  days  at  a  temperature 
of  25°  to  30°.  The  solution  is  then  heated  to  90°  and  after  cooling,  water  is 
added  until  the  original  weight  is  regained;  1  cc.  of  the  solution  must  then 
neutralize  40  to  42  cc.  0.1  N  alkali.  The  product  of  the  reaction  is  then  neu- 
tralized with  nickel  carbonate.  For  the  production  of  a  metal  catalyzer  0.6 
parts  Ni(NO2)2-6H2O  is  added,  together  with  a  pulverulent  inorganic  substance, 
e.g.,  pumice  stone  or  clay,  and  the  product  is  evaporated  to  dryness  and  decom- 
posed by  heating  with  exclusion  of  air.  To  obtain  the  oxide  catalyzer,  3  parts 
of  Ni(NO3)26H2O  are  added,  and  the  mass  is  evaporated  to  a  syrupy  consistence 
and  decomposed  by  heating. 

The  application  of  nickel  oleate  in  hydrogenating  oils,  as  described 
by  Ellis  ||  involves,  in  one  form,  the  thermal  decomposition  of  the 
oleate  in  an  oily  vehicle.  Beside  nickel  oleate  any  suitable  rretallo- 
organic  compound,  especially  one  soluble  in  oil  and  consisting  of  a 

*  British  Patent  No.  21,477,  September  23,   1913. 
t  J.  Ind.  Eng.  Chem.,  1915,  459. 
JSeifen.  Ztg.,   1915,  478. 

§  German  Patent  No.  292,894,  December  3,  1913;  Chem.  Abs.,  1917,  1530;  J.  S.  C. 
I.,  1916,  932. 

II  U.  S.  Patent  No.  1,217,118,  February  20,  1917. 


198  THE  HYDROGENATION  OF  OILS 

metal  united  to  a  weak  organic  acid  may  be  used  as  a  source  of 
catalytic  material.* 

By  heating  these  metallo-organic  compounds  decomposition  occurs  setting  free 
the  catalytic  material  in  a  state  of  extreme  subdivision  and  sometimes  forming 
a  colloidal  solution.  When  the  catalyzer  has  been  prepared  in  this  manner, 
it  is  admixed  with  the  oil  that  is  to  be  hydrogenated  and  hydrogen  is  introduced. 
In  those  cases  where  the  metallic  catalyzer  tends  to  dissolve  in  an  acid  fatty 
body  to  form  a  metallic  soap,  the  temperature  during  hydrogenation  may  be 
maintained  at  a  point  above  that  at  which  the  soap  is  unable  to  exist,  or  if 
previously  formed  may  be  decomposed.  A  temperature  of  about  10  degrees 
above  the  decomposition  point  is  recommended. 

Details  of  preparation  of  catalyzers  by  the  thermal  decomposition 
of  nickel  oleate  or  other  organic  compound  of  nickel  are  indicated  by 
Ellis,  f  A  catalyzer  may  be  made  by  the  reduction  of  nickel  acetate 
in  hydrogen.  J  A  mixture  of  nickel  formate  and  nitrate  when  heated 
gives  catalytic  nickel  material.!  Ellis  propose?  to  make  a  catalyzer 
concentrate  by  decomposing  in  oil,  an  excess  of  a  decomposable  com- 
pound of  nickel. 1 1  Nickel  carbonyl  may  be  used  in  this  case. 

In  the  hydrogenation  of  oils  with  colloidal  nickel  catalyzers,  Ellis 
recommends  that  especial  care  be  taken  to  free  the  hydrogen  gas 
emp^yed,  from  chlorine.^ 

A  catalyzer  for  hydrogenating  oils  is  prepared  by  the  Bremen-Besigheimer 
Oelfabriken,**  by  impregnating  kieselguhr  or  asbestos  with  a  solution  of  nickel 
acetate,  adding  a  limited  quantity  of  oil  and  heating  in  a  vacuum  at  a  temperature 
between  150  to  200°  C.  Finally  hydrogen  is  passed  through  the  mixture. 

Catalysts  such  as  finely  divided  reduced  nickel,  cobalt,  manganese,  copper,  etc., 
for  hardening  fats  are  prepared  by  Soc.  de  Stearinerie  et  Savonnerie  de  Lyon  and 
Berthon,tf  from  metallic  oxides  by  reduction  at  about  250°  C.  in  a  neutral  liquid 
medium  such  as  paraffin,  vaselin  or  heavy  petroleum  oil  with  the  addition  of  0.25 
to  0.5  per  cent  of  stearic  acid.  The  material  is  placed  in  vertical  tubes  and  heated 
to  about  250°  C.  The  metallic  oxide  is  then  added  and  hydrogen  is  injected.  Per- 
forated plates  are  arranged  in  the  tubes.  The  catalytic  metal  is  obtained  after 
about  2.5  to  3  hours  and  the  liquid  medium  is  separated  by  centrifuging. 

*  Patent  No.  1,217,118  was  involved  in  an  interference  with  the  Wimmer  and 
Higgins  Patent  No.  1,081,182  described  on  pages  47-8  and  priority  was  awarded  to 
ElKs  for  this  use  of  organic  compounds  of  nickel  in  the  hydrogenation  process.  In 
an  interference  with  Hausamann,  priority  was  also  to  awarded  Ellis  and  the  applica- 
tion on  which  Letters  Patent  No.  1,145,480  was  issued  to  Hausamann  July  6,  1915, 
was  involved  in  a  like  interference. 

fU.  S.  Patent  No.  1,251,201,  Dec.  25,  1917. 

J  Ellis  U.  S.  Patent  No.  1,251,203,  Dec.  25,  1917. 

§U    S.  Patent  No.  1,251,204,  Dec.  25,  1917,  to  Ellis. 

||  U.  S.  Patent  No.  1,251,202,  Dec.  25    1917. 

If  U.  S.  Patent  No.  1,184,086,  May  23,  1916. 

**  German  Patent  304,043,  August  18,  1912. 

ft  British  Patent  107,004,  May  19,  1917  and  107,969,  June  25,  1917;  J.  S.  C.  I.,  1918 
431 A  and  553 A. 


CHAPTER  VIII 
THE  BASE  METALS  AS   CATALYZERS.— Continued 

NOTES  ON  NICKEL  OXIDE  CATALYZERS 

Bedford  and  Erdmann  *  assert  that  metallic  oxides  can  be  pro- 
duced in  an  extremely  finely-divided  and  voluminous  form  by  pre- 
paring a  concentrated  aqueous  solution  of  a  nitrate,  mixing  the  same 
with  an  organic  compound  which  is  soluble  in  water  and  rich  in 
carbon  and  subsequently  decomposing  by  heat.  A  strong  evolu- 
tion of  gas  takes  place  during  the  combustion  of  the  organic  sub- 
stance with  the  nitrate  and  the  metallic  oxide  swells  up  to  a  large 
volume,  assuming  the  form  of  a  dust,  while  the  whole  of  the  carbon 
present  in  the  organic  compound  is  removed  by  the  combustion. 
On  reducing  with  hydrogen  at  200°  to  300°,  the  metallic  oxides 
prepared  according  to  this  method  can  be  converted  into  the  corre- 
sponding voluminous  and  catalytically  active  metals. 

Example:  Nitric  acid  of  specific  gravity  of  1.42  is  diluted  with  an 
equal  volume  of  water  and  to  the  diluted  acid  pure  metallic  nickel 
is  added.  When  the  resulting  reaction  is  completed,  the  whole  is 
heated  to  boiling  for  about  two  hours  in  the  presence  of  an  excess 
of  nickel  in  order  to  neutralize  completely  the  nitric  acid  present 
and  to  precipitate  any  iron  which  may  occur  as  hydrated  oxide  of 
iron.  The  clarified  nickel  nitrate  solution  is  evaporated  until  its 
specific  gravity  is  1.6  and  for  each  liter  of  this  liquid  (corresponding 
to  250  g.  of  nickel)  are  stirred  in  180  g.  of  powdered  cane  sugar. 
This  solution  is  run  in  portions  into  a  muffle  of  any  suitable  con- 
struction heated  to  a  dull  red  heat  and  the  heating  of  each  portion  is 
continued  until  no  more  fumes  escape.  The  voluminous  nickel 
oxide  thus  formed  is  removed  from  the  muffle  by  means  of  a  scraper 
and  a  fresh  portion  of  the  solution  run  in. 

By  means  of  the  process,  cobalt  oxide,  iron  oxide  and  other  oxides 
of  the  heavy  metals  which  may  be  used  for  catalytic  purposes,  can 
be  produced  in  a  light  voluminous  and  catalytically  active  form  and 
are  well  adapted  both  in  the  form  of  oxide  and  in  the  form  of  metal 

*  U.  S.  Patent  No.  1,200,696,  October  10,  1916. 
199 


200  THE  HYDROGENATION  OF  OILS 

as  catalytic  material  for  adding  hydrogen  to  unsaturated  organic 
compounds.  Other  forms  of  sugar,  or  starch,  dextrin,  gum  arabic 
or  tartaric  acid  may  be  used  in  place  of  cane  sugar. 

Normann  *  states  that  up  to  the  present  time  there  is  no  positive  proof  of 
the  existence  of  nickel  suboxide  in  catalytic  nickel  material.  The  reaction  of  the 
reduced  catalytic  substance  with  phosphomolybdic  acid  as  employed  by  Erdmann 
is  by  no  means  a  specific  test  for  nickel  suboxide  but  is  exhibited  by  many 
reduced  bodies  such  as  finely-divided  metallic  nickel.  The  method  of  testing 
electrical  conductivity  used  by  Erdmann  is  not  proof  of  the  absence  of  metallic 
nickel  f-  Erdmann's  contention  that  the  blackening  and  fine  distribution  of 
the  catalyzer  in  oil  when  under  initial  reducing  conditions  indicates  the  presence 
of  suboxide  of  nickel  is  regarded  as  groundless.  Finely-divided  metallic  nickel 
is  black  and  it  is  known  that  nickel  carbonyl  when  decomposed  in  oil  yields  an 
inky  black  liquid.  Normann  very  pointedly  observes  that  he  might  just  as  well 
claim  the  blackening  was  a  "  proof  "  of  the  formation  of  metallic  nickel  as  of 
the  suboxide. 

The  failure  of  Bedford  and  Erdmann  to  observe  the  formation  of 
metallic  nickel  when  employing  the  oxide  is  due  to  erroneous  methods 
of  examination,  according  to  Normann  and  Pungs.  {  It  is,  of  course, 
of  importance  to  the  further  development  of  the  hydrogenation 
process  to  settle  the  question  whether  the  metal  or  its  oxide  is  the 
real  hydrogen  carrier,  Normann  and  Pungs  endeavored  to  find  a 
reliable  method  of  determining  metallic  nickel  and  investigated  the 
products  obtained  with  nickel  oxide,  the  carbonate,  also  the  formate 
and  other  organic  salts  of  nickel.  The  results  obtained  with  nickel 
oxide  likewise  apply  to  these  nickel  salts. 

For  the  experimental  work  300  cc.  round-bottomed  flasks  having  a  gas  inlet 
tube  at  the  bottom  were  used.  The  bulk  of  the  flask  was  almost  completely 
immersed  in  an  oil  bath  heated  to  255°  C.  Various  fatty  oils  were  hydrogenated, 
including  olive,  linseed,  sesame,  whale  and  refined  cotton  oil  which  had  been 
blown  with  superheated  steam  under  diminished  pressure.  The  kind  of  oil 
employed  made  no  difference  as  regards  the  formation  of  metallic  nickel;  100  g. 
of  oil  were  heated  in  the  flask  to  200°  C.  and  hydrogen  at  the  rate  of  2  liters 
per  minute  were  passed  through  the  oil,  thereby  causing  brisk  agitation.  One 
gram  of  nickel  oxide  was  then  added  and  the  temperature  raised  to  255°  C. 
Small  samples  were  withdrawn  from  time  to  time  and  the  melting-point  deter- 
mined. When  a  melting-point  of  45°  C.  was  reached,  which  usually  required 
two  to  three  hours  time,  the  nickel  material  was  collected  and  tested  for  the 
presence  of  the  free  metal.  Both  pure  and  technical  nickel  oxide  were  examined 
and  the  different  grades  of  the  oxide  were  found  to  be  more  or  less  efficient  in 
hardening  oil  and  substantially  alike  as  regards  the  formation  of  free  nickel. 

Determination  of  Electrical  Conductivity.  The  terminals  of  a  small  dry  bat- 
tery were  connected  each  to  a  metal  plate,  so  that  the  circuit  would  be  closed  on 

*  Seifen.  Ztg.,  1915,  47  and  191. 

t  See  Normann  and  Pungs,  Chem.  Ztg.,  1915,  No.  6  and  7/8. 

$  Chem.  Ztg.,  1915,  29. 


THE  BASE  METALS  AS  CATALYZERS 


201 


contact  of  the  two  metal  plates.  In  the  circuit  was  placed  a  galvanometer  or  an 
electric  bell.  A  sheet  of  mica  with  an  opening  1  centimeter  square  was  placed 
between  the  plates,  thereby  insulating  them.  In  testing  conductivity  a  small 
amount  of  the  powder  was  placed  in  the  square  opening,  in  contact  with  a  metal 
plate  and  the  second  plate  pressed  on  to  the  mass.  The  deflection  of  the  gal- 
vanometer indicates  the  relative  conductivity  and  when  high,  enough  current 
may  pass  to  ring  the  bell.  Lack  of  deflection  of  the  galvanometer  is,  however, 
no  indication  of  the  absence  of  metallic  nickel.  A  catalyzer  used  by  the  Oel- 
werke  Germania  of  Emmerich  and  prepared  by  reduction  with  hydrogen  of 
nickel  material  supported  on  an  inorganic  non-conducting  pulverulent  carrier 
did  not  prove  to  be  a  conductor.  When  nickel  oxide  is  used  for  oil  hardening, 
and  the  resulting  black  powder  separated  by  deposition  and  washing  with  ben- 
zol, in  some  cases  the  used  catalyzer  conducts  electricity,  while  in  other  cases  it 
does  not  exhibit  this  property.  Doubtless  the  conductivity  is  dependent  on  the 
actual  metal  content  of  the  powder.  It  is  conceivable  that  each  particle  of 
nickel  oxide  is  not  at  once  fully  reduced  to  the  metallic  state  but  that  super- 
ficial reduction  first  occurs  and  by  continued  contact  with  hydrogen,  the  con- 
tent of  free  metal  increases.  The  dependence  of  the  degree  of  conductivity  on 
the  duration  of  exposure  to  hydrogen  and  consequent  variation  in  metal  content 
is  shown  in  the  tables  below.  The  percentage  of  nickel  is  calculated  on  the 
amount  of  hydrogen  liberated  by  dilute  sulphuric  acid. 

CONDUCTIVITY  OF  REDUCED  NICKEL  OXIDE 
KAHLBAUM'S  NICKEL  OXIDE  IN  COTTONSEED  OIL 


Time  of  Hardening. 

Total  Nickel  in 
Used  Catalyzer. 

Free  Nickel  in 
Used  Catalyzer. 

Iodine  No. 
of  the 
Hardened  Fat. 

Conductivity. 

Two  hours  
Two  hours,  fifty  minutes  . 
Four  hours  

79.4 

85.2 

12.7 
41.2 

63 
21.2 
9  7 

none 
good 
good 

Seven  hours  

88  1 

53  0 

3  85 

good 

Thus  it  appears  that  the  conductivity  becomes  manifest  between  12  per  cent 
and  41  per  cent  of  free  nickel.  The  nickel  content  of  the  above-mentioned 
commercial  catalyzer  (Oelwerke  Germania)  of  a  non-conducting  nature  lies 
between  these  limits. 

Linseed  oil  was  used  in  the  1  per  cent  nickel  oxide  tests,  and  in  all  the  others 
cottonseed  oil  was  employed. 

By  a  magnetic  method  of  separation  similar  to  that  used  by  Erdmann  *  who 
obtained  negative  results,  Normann  and  Fungs  succeeded  in  isolating  the  better 
conducting  portions  of  catalytic  material  having  a  low  content  of  free  nickel. 
The  oil  and  catalyzer  mixture  after  treatment  with  hydrogen,  was  cooled  to 
140°  C.  and  a  strong  electro-magnet  moved  about  in  the  oil  thus  attracting  the 
nickel  particles  which  were  removed  and  washed  with  benzol.  The  nickel 
material  was  collected  with  the  magnet  and  introduced  into  fresh  benzol  and  the 
operation  repeated  several  times.  A  fractionation  of  metallic  nickel  from  nickel 

*  Journ.  Prakt.  Chem.,  1913,  437. 


202 


THE  HYDROGENATION   OF  OILS 


oxide,  although  the  latter  is  somewhat  magnetic,  is  thus  obtained.  The  nickel 
powder  is  well  washed  with  ether  and  dried  in  a  drying  oven.  It  is  then  ready 
for  a  conductivity  determination. 

CONDUCTIVITY  OF  REDUCED  NICKEL  COMPOUNDS. 


Catalyzer  Material. 

Melting-point  of 
Resulting  Fat. 

Conductivity. 

Nickel  oxide,  \  per  cent  Kahlbaum  

28 

32.2 

none 
none 

Nickel  oxide,  1  per  cent  Kahlbaum  \ 

45.6 
53.6 
liquid 
salve-like 

good 
good 
none 
none 

Nickel  oxide,  Merck. 

27. 
46.2 
45  5 

good 
good 
good 

Nickel  carbonate  

49  8 

noticeable 

Nickel  hydroxide. 

45  9 

noticeable 

Nickel  formate    5  per  cent 

good 

Nickel  formate,  3  per  cent  

45.5 

good 

Nickel  formate,  1  per  cent 

good 

The  powder  is  pressed  between  the  metallic  plates  preferably  gently  rubbing 
to  secure  good  contact.  Too  violent  rubbing  tends  to  reduce  conductivity, 
which  is  explained  on  the  supposition  that  the  particles  by  partial  reduction 
acquire  a  skin  of  metallic  nickel  and  these  particles  show  metallic  conductivity. 
If  crushed,  a  mixture  of  conducting  and  non-conducting  material  is  produced 
and  the  latter  obstructs  the  flow  of  the  current. 

Extremely  fine  metal  powders  conduct  electricity  poorly  or  not  at  all.  Nor- 
mann  and  Pungs  frequently  observed  a  lack  of  conductivity  in  products  which 
were  prepared  under  conditions  inevitably  yielding  a  substantial  proportion  of 
free  metal,  and  which,  indeed,  afforded  a  positive  test  for  nickel  by  the  car- 
bonyl  reaction.  This  was  noted  particularly  when  using  nickel  carbonate.  On 
bringing  a  magnet  near  a  mass  of  warm  fat  containing  the  products  of  the  action 
of  hydrogen  on  'the  carbonate,  no  particles  were  attracted,  but  a  peculiar  light 
reflex  was  noted  which  changed  as  the  magnet  was  moved  about,  showing  mag- 
netic orientation  of  the  suspended  particles.  On  microscopic  examination,  these 
supposedly  granular  particles  were  found  to  be  rod  shaped.  Evidently  these 
minute  rods  became  magnetically  polarized  and  changed  position  in  the  oil  to 
accord  with  the  pole  of  the  magnetic  source  presented.  The  product  was  allowed 
to  stand  in  oil  overnight  and  the  following  morning  it  was  treated  with  hydro- 
gen for  one-half  hour  at  200°  C.  Then  it  was  found  that  the  fine  particles  had 
formed  into  aggregates  which  were  easily  attracted  by  the  magnet  and  conducted 
electricity. 

A  qualitative  test  of  conductivity  was  not  deemed  sufficient  proof  of  the 
presence  of  free  metal,  as  metallic  oxides,  such  as  nickel  oxide,  even  when  per- 
fectly dry,  show  a  slight  degree  of  conductivity.  By  strongly  rubbing  nickel 
oxide  between  the  pole  plates  a  considerable  deflection  of  the  galvanometer 


THE  BASE  METALS  AS  CATALYZERS 


203 


frequently  was  noted.  Metallic  oxides  appear  to  contain  particles  of  relatively 
good  conductivity  which  contact  on  rubbing  and  provide  conducting  zones. 
Normann  and  Pungs  made  a  number  of  determinations  of  electrical  resistance 
with  the  Wheatstone  bridge  on  various  oxides,  before  and  after  employment  in 
the  hardening  process.  A  centimeter  square  opening  in  a  mica  plate  between 
two  metal  plates  was  used  in  these  as  in  the  preceding  determinations. 

MEASUREMENTS  OF  RESISTANCE  IN  OHMS 


NICKEL  OXIDE  (ic). 
KAHLBAUM. 

NICKEL  OXIDE  (ous). 
KAHLBAUM. 

NICKEL  OXIDE. 
MERCK. 

Nickel 
Carbonate 
After  Fat 
Hardening. 

Before. 

After. 

Before. 

After. 

Before. 

After. 

8000 
8500 
900 
9000 

2.1 
2.5 
•      20. 
70. 
30. 
0.7 
0.8 

over 
50,000 

3 
1.5 
100 
90 
20 
15 
16 

over 
50,000 

15 
18 
100 
10 

1 



These  measurements  show  a  decided  difference  in  conductivity  before  and 
after  fat  hardening. 

Bedford  and  Erdmann  have  referred  to  a  suboxide  of  nickel  reported  by  Moore  * 
in  support  of  the  contention  that  the  suboxide  is  formed  in  the  hydrogenation 
process.  Normann  and  Pungs  prepared  a  suboxide  according  to  Moore's  pro- 
cedure and  found  it  lacking  in  conductivity.  However  after  using  this  com- 
pound for  oil  hardening  the  conductivity  was  excellent  indicating  reduction  to 
the  metallic  state. 

Analytical  Determination  of  Free  Nickel.  The  analytical  determination  returns 
a  higher  content  of  nickel  than  the  conductivity  indicates,  and  invariably  more 
nickel  is  found  than  would  correspond  to  the  suboxide  formula.  The  following 
examination  was  made: 

1.  Two  hundred  and  fifty  grams  of  olive  oil  were  hardened  at  250°  C.  using 
2.5  g.  of  nickel  oxide  prepared  from  the  nitrate.  The  fat  melted  at  55.2°  C. 
and  possessed  an  iodine  number  of  31.  The  catalyzer  was  allowed  to  settle 
and  was  repeatedly  washed  with  benzine  and  benzol.  The  last  portions  of  the 
solvent  were  removed  with  carbon  dioxide.  To  remove  occluded  hydrogen  the 
catalyzer  was  exposed  for  one  hour  to  a  vacuum  of  1  mm.  mercury.  The  nickel 
product  was  treated  with  sulphuric  acid  and  the  evolved  hydrogen  measured. 
Some  fatty  material  separated  when  the  acid  was  added  and  correction  was 
made  for  this. 

Weight  of  substance  taken 0.2313   g. 

Fat  separated 0 . 1204 


Fat  free  catalyzer 0 . 1109  g. 

*  Chem.  News,  1893,  68,  295;    1895,  71,  81. 


204  THE  HYDROGENATION  OF  OILS 

With  sulphuric  acid,  36.4  cc.  of  hydrogen  at  23°  C.  and  756  mm.  were  evolved 
corresponding  to  a  content  of  77.4  per  cent  free  nickel.  If  the  formula  of  the 
suboxide  is  regarded  as  NisO  and  there  action  as  Ni3O+3H2SO4  =  3NiSO4H-H2O 
+2H2  then  the  hydrogen  actually  found  represents  a  content  of  125  per  cent 
nickel  suboxide  or  114.6  per  cent  total  nickel.  If  the  formula  of  the  suboxide  is 
considered  as  Ni2O  *  the  results  calculated  on  the  hydrogen  gas  evolved  would  be 
173.5  per  cent  NiO  and  152.7  per  cent  total  nickel,  all  of  which  figures  are,  of 
course,  impossible. 

2.  One  hundred   grams   edible    sesame    oil   were    hardened    with    nickel    oxide 
(ous)  Kahlbaum  at  a  temperature  of  about  255°  C.  to  a  melting-point  of  48.1°  C. 
The  catalyzer  was  dissolved  in  sulphuric  acid,  the  hydrogen  measured  and  the 
total  nickel  determined  electrolytically.     Results:    0.1706   total  nickel,   62.1    cc. 
hydrogen  at  26°  C.  and  774  mm.  corresponding  to  86.5  per  cent  of  nickel.     If 
figured  as  Ni3O  the  nickel  content  would  be  128.7  per  cent. 

3.  Five  hundred  grams  sesame  oil  were  hardened  with  5  g.  nickel  oxide  (ous) 
Kahlbaum  to  a  melting-point  of  52°  C.     The  catalyzer  was  removed  by  means 
of  a  magnet.     On  treatment  with  sulphuric  acid  some  fatty  matter  and  green 
nickel    oxide    remained    undissolved.     The    hydrogen    evolved    corresponded    to 
76.8  per  cent  nickel  but  if  a  suboxide  Ni3O  were  assumed  to  be  responsible  for 
this  amount  of  hydrogen,  124.6  per  cent  of  the  suboxide  would  be  required. 

4.  Five  hundred  grams  of  seasme  oil  were  hardened  to  a  melting-point  of  53.5, 
using  5  g.  nickel  oxide  (ous)  Kahlbaum  and  the  catalyzer  treated  as  in  deter- 
mination No.  3.     The  hydrogen  given  off  was  equivalent  to  71.4  per  cent  nickel. 
Correction  was  made  for  undissolved  nickel  oxide  and  fatty  residue.     Calculated 
to   Ni3O,   the  percentage  of  the   latter  would  be   115.6.     Normann   and  Fungs 
consider  these  determinations  to  fully  establish  the  fact  of  formation  of  metallic 
nickel  in  all  cases,  even  if  it  be  assumed  that  some  suboxide  is  formed.     They 
find,  however,  no  basis  for  such  an  assumption. 

The  Nickel  Carbonyl  Test  for  Metallic  Nickel.  In  testing  nickeliferous  cata- 
lyzers for  free  nickel  by  the  carbonyl  reaction  Normann  and  Pungs  f  note  that 
certain  precautions  must  be  observed.  The  greatest  care  should  be  taken  to 
have  the  carbon  monoxide  employed  very  pure  and  thoroughly  dry.  Normann 
and  Pungs  prepared  the  monoxide  by  allowing  concentrated  formic  acid  to  drop 
into  concentrated  sulphuric  acid  heated  by  a  water-bath.  The  gas  was  dried 
by  passage  through  sulphuric  acid  and  then  over  soda  lime  and  solid  caustic 
soda. 

The  carbonyl  reaction  is  extraordinarily  sensitive  to  the  presence  of  air. 
Simply  by  pouring  the  hardened  fat  and  catalyzer  from  one  vessel  to  another, 
suffices  to  nullify  the  reaction.  Accordingly,  after  hardening,  the  fat  and  catalyzer  is 
cooled  to  90°  to  100°  C.  in  a  weak  current  of  hydrogen.  Then  the  vessel  is  placed 
in  a  water-bath  at  90°  to  92°  C.  and  the  hydrogen  replaced  by  carbon  monoxide. 
The  gases  leaving  the  reaction  flask  are  passed  through  a  hard  glass  tube  which 
is  heated  at  one  point.  Nickel  carbonyl  is  decomposed  and  forms  a  mirror 
on  the  glass  walls  in  the  heated  zone.  To  obtain  good  adherence  of  nickel  the 
tube  must  be  thoroughly  clean.  The  separation  of  nickel  is  not  quantitative. 
Some  carbonyl  escapes  decomposition  in  the  heating  zone,  as  may  be  shown  by 
igniting  the  issuing  gas.  The  flame  is  colored  yellow  or  if  the  amount  of  car- 

*Bellucci  and  Correlli,  Z.  anorg.  Chem.,  1914,  88. 
t  Chem.  Ztg.,  1915,  41. 


THE  BASE  METALS  AS  CATALYZERS 


205 


bonyl  is  extremely  minute  the  color  is  a  pale  blue.     Only  a  few  minutes  suffice 
to  secure  a  heavy  nickel  mirror. 

NICKEL  CARBONYL  REACTION  ON  CATALYZERS. 


Oil. 

Catalyzer. 

Melting- 
point  of  the 
Hardened 
Fat. 

Nickel 
Mirror. 

Cotton  oil.             .... 

5  per  cent  basic  nickel  formate 

50  8 

marked 

Cotton  oil. 

5  per  cent  basic  n:ckel  formate 

51  2 

Cotton  oil  

1  per  cent  nickel  carbonate 

49  8 

marked 

Cotton  oil  

^  per  cent  oxide  (Erdmann) 

46  2 

marked 

Purp  linseed  oil 

^  per  cent  oxide  (Erdmann) 

42  4 

Whale  oil. 

\  per  cent  oxide  (Erdmann) 

46  8 

marked 

Linseed  oil  

5  per  cent  oxide  (Kahlbaum) 

42  5 

marked 

Linseed  oil  

2  per  cent  oxide  (Merck) 

40  6 

marked 

Linseed  oil 

5  per  cent  oxide  from  nitrate 

40  6 

marked 

Linseed  oil  

§  per  cent  oxide  (Kahlbaum) 

40  2 

marked 

If  hydrogenation  is  allowed  to  progress  to  a  lesser  degree,  the  mirror  appears 
with  the  carbonyl  test.  For  example,  olive  oil  was  hardened  to  a  melting-point 
of  only  17°  C.  and  a  positive  test  for  nickel  was  obtained.  If  fat  hardening  is 
carried  out  at  a  temperature  below  that  prescribed  by  Erdmann,  or  not  over 
230°  C.,  blackening  of  the  green  nickel  oxide  does  not  occur,  the. color  changing 
only  to  a  greyish  green.  The  iodine  number  of  olive  oil,  after  3|  hours  hydro- 
genation under  these  conditions,  fell  but  one  or  two  units.  The  carbonyl  test 
was  positive  although  very  weak.  A  blank  test  with  the  same  nickel  oxide  in 
fresh  oil  and  without  treatment  with  hydrogen,  maintained  at  90°  C.,  while 
carbon  monoxide  was  passed  through,  showed  that  nickel  oxide  was  not  reduced 
by  the  monoxide  under  these  conditions. 

Since  Erdmann  has  suggested  that  the  reduction  of  nickel  oxide  may  be 
brought  about  by  aldehydes  contained  in  the  oil,  Normann  and  Pungs  tested 
the  reducing  effect  of  formaldehyde  and  benzaldehyde,  two  of  the  most  powerful 
reducing  aldehydes.  They  heated  a  mixture  of  edible  oil,  aldehyde  and  nickel 
oxide  on  an  oil  bath  at  225°  C.,  without  introducing  hydrogen.  No  reduction 
of  the  oxide  was  noted;  in  one  case,  olive  oil,  benzaldehyde  and  green  nickel 
oxide  were  heated  to  about  250°  for  four  hours,  using  a  reflux  condenser;  but  no 
blackening  of  the  oxide  was  perceptible.  The  likelihood  of  reduction  by  the  alde- 
hydes of  fatty  oils,  therefore,  appears  to  be  remote. 

In  the  table  below  the  results  of  the  carbonyl  reaction  at  a  temperature  of 
50°  C.  are  given  when  employing  olive  oil  of  iodine  No.  82,  freed  from  aldehydes 
by  the  silver  nitrate  method  of  Becchi,  and  hydrogenating  at  a  temperature  of 
250°  C.  in  the  first  four  tests  and  at  230°  C.  in  the  remaining  tests. 

Thus,  at  50°  C.  as  well  as  at  90°  C.,  the  carbonyl  reaction  is  obtained  from 
catalyzer  in  oil.  Even  at  30°  C.  the  carbonyl  is  slowly  formed.  At  30°  C.  the 
necessary  contact  of  the  monoxide  with  the  relatively  thick  oil  is  difficult  to 
bring  about. 

An  endeavor  was  made  to  make  the  carbonyl  test  a  quantitative  one.  To 
this  end,  the  glass  tube  in  which  the  nickel  carbonyl  was  decomposed,  was  filled 


206 


THE  HYDROGENATION  OF  OILS 


with  fragments  of  porcelain  and  was  heated  in  two  or  more  places.  It  was  then 
noted  whether  or  not  at  the  place  of  heating  most  remote  from  the  point  of 
entry  of  the  carbonyl,  any  nickel  was  deposited.  The  exit  gases  were  ignited 
and  the  color  of  the  flame  noted.  It  should  be  a  pure  blue.  From  1  g.  of 
catalyzer  held  at  a  temperature  of  90°  C.  for  four  hours  0.05  g.  of  nickel  were 
obtained.  A  second  test  conducted  for  four  days  gave  0.07  g.  nickel.  Even 
then  the  reaction  had  not  been  completed.  Nickel  carbonyl  was  still  being 
formed  in  the  oil. 


NICKEL  CARBONYL  FORMATION  AT  50°  C. 


Catalyzer. 

Melting- 
point 
of  the 
Hard- 
ened 
Fat. 

Iodine 
No. 

Carbonyl  Test. 

1  per  cent  nickel  oxide  (ic)  Kahlbaum  .... 
1  per  cent  nickel  oxide  (ic)  Kahlbaum.  .  .  . 
1  per  cent  nickel  oxide  (ous)  

15.5 
49.6 
27  0 

68.4 
37.1 

67  4 

Heavy  nickel  mirror 
Heavy  nickel  mirror 
Heavy  nickel  mirror 

1  per  cent  nickel  oxide  (ous). 

49  8 

38  0 

Heavy  nickel  mirror 

1  per  cent  nickel  oxide  (ous)  Temp.  230°.  .  . 
1  per  cent  nickel  oxide  (ous)  Temp.  230°.  .  . 

Liquid 
Liquid 

78.0 
79.0 

Distinct  mirror 
Weak  but  distinct  mirror 

If  the  residue  of  nickel  in  the  oil  is  regarded  as  negligible,  Normann  and  Pungs 
assume  the  hardening  to  have  been  carried  out  with  a  catalyzer  consisting  of 
about  7  per  cent  of  metallic  nickel  on  upwards  of  90  per  cent  of  nickel  oxide 
serving  as  a  carrier.  The  question  then  arose  as  to  the  possibility  of  so  small  a 
proportion  of  nickel  effecting  the  degree  of  hydrogenation  noted.  Normann  and 
Pungs  regard  the  question  as  answered  as  a  result  of  their  practical  experience. 
It  is  stated  that  a  catalyzer  of  this  composition,  when  carefully  and  skillfully 
prepared,  gives  good  results  not  only  in  the  laboratory  but  also  on  the  large  scale. 
From  repeated  use  more  nickel  is  likely  to  be  reduced  as  a  result  of  the  con- 
tinued contact  with  hydrogen. 

A  nickel-kieselguhr  catalyzer  was  prepared  by  reduction  at  450°  to  500°  C. 
at  which  temperature  the  existence  of  a  suboxide  is  regarded  as  entirely  excluded. 
The  content  of  free  nickel,  calculated  from  a  determination  of  the  volume  of 
hydrogen  evolved  by  sulphuric  acid  was  4.2  per  cent.  By  the  addition  of  only 
1  per  cent  of  this  catalyzer  to  refined  sesame  oil,  the  melting-point  was  raised 
to  45°  C.  on  hydrogenating  for  one  hour.  Normann  and  Pungs  do  not  record 
the  amount  of  nickel  computed  from  the  mixing  formula  of  this  catalyzer  so 
that  it  does  not  appear  whether  or  not  this  calculated  proportion  checks  with  the 
result  of  the  hydrogen  evolution  determination. 

In  every  instance,  the  catalyzer  material,  which  before  hardening,  did  not 
contain  free  metal,  after  hardening,  showed  the  presence  of  the  metal,  hence, 
irrespective  of  the  question  of  formation  of  nickel  suboxide  or  other  assumed 
reduction  product  intermediate  nickel  oxide  and  the  metal,  it  is  concluded  that 
fat  hardening  does  not  occur  in  the  absence  of  the  free  metal  and  that  some  sub- 
stance other  than  the  free  metal  is  an  active  catalytic  agent,  as  contended  by 
Erdmann,  has  not  been  proven.  . 


THE  IUSE   METALS  AS  CATALYZERS  207 

Metallic  Nickel  vs.  Nickel  Cxiue.  In  the  discussion  between 
Normann  and  Erdmann  over  nickel  borate  certain  comments  by  the 
latter  *  are  of  interest  in  spite  of  the  controversial  attitude  of  Erd- 
mann. He  states: 

(1)  Through  mere  heating  of  finely-divided,  freshly-reduced  nickel  in  oil  with 
or  without  the  presence  of  hydrogen  an  inky  black  liquid  never  is  formed. 

Considering  the  conditions  under  which  reduction  of  a  higher  oxide  of  nickel 
in  oil  takes  place,  nickel  suboxide  has  at  least  an  equal  chance  of  forming  as 
metallic  nickel  and  it  is  logical  to  conclude  that  the  suboxide  is  responsible  for 
the  black  coloration. 

(2)  Dark-colored   suspensions  of  colloidal  nickel  may  be  obtained  by  electrical 
comminution  of  the  metal  in  oil.     When  this  suspended  material  is  separated  it 
is  found  to  conduct  electricity  like  a  metal  quite  unlike  nickel  oxide  suspensions. 

(3)  As   hydrogen    carriers,    such    colloidal    suspensions    of   metallic   nickel   are 
practically  of  no  value.     For  this  reason  Shukoff's  nickel  carbonyl  process  f  has 
not  come  into  use. 

Erdmann  then  proceeds  to  criticize  Normann's  view  that  the  activity  of  a 
metallic  catalyzer  resides  in  an  important  measure  in  its  degree  of  subdivision 
especially  the  statement  by  the  latter  that  "  For  this  reason,  carriers  for  the 
metallic  nickel  have  come  into  use.  Thus,  it  is  possible  to  prepare  metallic 
catalyzers  which  are  almost  without  activity,  and  again,  others  which  have 
extraordinary  efficiency."  Obviously,  Erdmann  states,  the  fine  nickel  powder 
obtained  by  reduction  in  a  current  of  hydrogen  as  set  forth  in  the  Leprince  and 
Siveke  Patent  No.  141,029  belongs  to  the  first  category — the  almost  inactive 
class.  But  whether  the  fine  subdivision  alone  of  the  catalytic  is  responsible  for 
its  high  degree  of  activity  is  a  consideration  which  Erdmann  declines  to  discuss. 

The  greater  activity  of  once  used  nickel  oxide  catalyzer  as  compared  with  the 
original  oxide  is  due  to  the  formation  of  metallic  nickel,  according  to  Oelwerke 
Germania.t  By  repeated  use  the  oxide  catalyzer  operates  satisfactorily  at  the 
same  temperature  as  the  free  metal  catalyzer  and  the  high  temperature  of  250° 
required  in  the  first  instance  is  necessary,  not  for  hardening,  but  for  the  forma- 
tion of  free  nickel. 

The  manufacture  of  nickel  oxide  masses  from  granular  nickel  compound  such 
as  the  carbonate,  by  igniting  in  a  reducing  gas  atmosphere  is  described  by 
Hoyer.§  For  the  production  of  the  granular  nickel  compound  pulverized  nickel 
carbonate  is  moistened  with  water  so  that  it  bakes  together,  and  after  drying  is 
cut  into  grains.  These  grains  are  rounded  off,  compacted  and  after  drying, 
are  reduced  in  illuminating  gas.  The  ignition  must  not  be  too  strong,  sinc£ 
otherwise  the  grains  become  too  hard. 

Paal  and  Brunjes  state  that  sodium  protalbinate  and  lysalbinate  exert  only  a 
relatively  slight  protective  action  on  sols  of  nickel  hydrate  and  that  it  is  impos- 
sible to  obtain  sols  of  high  nickel  hydrate  content  by  their  use.  The  prepara- 
tion of  stable  hydrosols  containing  6  to  10  per  cent  nickel  hydrate  is  described. || 

*  Seifen.  Ztg.,  1915,  288. 

t  German  Patent  No.  241,823. 

j  Seifen.  Ztg.,  1914,  645. 

§  German  Patent  No.  277,743,  July  17,  1913;  Chem.  Abs.,  1915,  761. 

II  Chem.  Abs.,  1914,  3275;   Ber.,  47,  2200-2. 


208  THE  HYDROGENATION  OF  OILS 

Robson  notes  *  that  the  use  of  nickel  oxide  as  a  catalyzer  is  defended  by  the 
Industria  Saponica  of  Milan,  which  asserts  that  the  use  of  metallic  nickel  can 
never  achieve  commercial  importance.  This  curious  pronouncement  is  made  on 
two  grounds.  One  is  that  the  claim  as  to  the  effect  of  impurities  in  the  oil  upon 
the  nickel  is  correct,  as  even  if  the  hydrogen  used  is  chemically  pure,  traces  of 
albuminous  bodies  left  in  the  oil  by  defective  refining  check  the  efficiency  of 
the  nickel  materially,  causing  the  action  to  be  slow  and  giving  a  diminished  out- 
put, with  a  largely  increased  amount  of  nickel.  The  other  ground  is  that  the 
activity  of  the  metal  is  diminished  seriously  even  if  the  fat  to  be  hardened  is 
pure,  by  the  presence  of  impurities  in  the  hydrogen,  especially  traces  of  chlorine 
or  of  sulphuretted  hydrogen. 

For  preparing  a  catalyzer  for  hydrogenation  of  oils  and  fats,  the  Suzuki-Shoten 
Co.f  treats  corn  husks,  sawdust,  or  insoluble  organic  substances  rich  in  carbon  with 
a  mineral  acid  and  works  the  mixture  into  a  paste  with  nickel,  iron  or  copper 
material.  This  paste  is  ignited  to  produce  a  porous  carbon  which  retains  metallic 
oxides  in  a  highly  active  state. 

British  Patent  No.  29,981  of  1912  for  An  Improved  Process  for  the  Prepara- 
tion of  Saturated  Fatty  Acids,  their  Glycerides  and  other  Esters,  issued  to 
Bedford,  Williams,  Erdmann  and  Hydroil  Limited,  indicates  that  on  further 
study  of  the  process  protected  by  British  Patent  No.  29,612  of  1910,  it  has  been 
found  that  nickel  suboxide  is  especially  suitable  as  a  reducing  catalyst  for  the 
addition  of  hydrogen  to  unsaturated  fatty  acids  or  their  glycerides.  The  patent- 
ees state  that  nickel  suboxide  is  one  of  the  lower  oxides  of  nickel  and  its  formula 
has  not  yet  been  definitely  settled.  Muller  J  and  Glaser  §  ascribe  to  it  the  formula 
Ni2O,  but  Thomas  Moore,  who  has  more  than  anyone  else  examined  this  com- 
pound in  detail,  gives  it  the  formula  Ni3O-2H2O.|| 

Although  its  formula  is  uncertain  the  suboxide  possesses  characteristic  prop- 
erties. It  is  strongly  magnetic,  gives  off  hydrogen  on  treatment  with  dilute 
mineral  acid,  evolves  nitric  oxide  fumes  even  in  the  cold.  While  it  is  distin- 
guished by  these  properties  from  all  other  nickel  oxides  it  is  sharply  distin- 
guished from  metallic  nickel  in  that  it  possesses  no  electric  conductivity,  thus,  if 
a  pastille  be  pressed  out  of  nickel  suboxide,  the  polar  ends  of  two  wires  be 
inserted  therein  and  a  source  of  electric  energy  at  an  E.M.F.  of  24  volts  be 
included  in  the  circuit  no  current  is  indicated  by  a  sensitive  galvanometer  in 
the  circuit  even  when  the  wires  are  only  separated  from  one  another  by  a  dis- 
tance of  1  millimeter. 

It  is  further  found  that  nickel  suboxide  is  characterized  by  the  property  of 
giving  colloidal  solutions.  The  red  solutions  obtained  according  to  Moore  on 
reducing  an  aqueous  solution  of  potassium  nickel  cyanide  with  sodium  amalgam 
or  zinc  coated  with  copper  or  by  means  of  an  electric  current  contain  the  sub- 
oxide  in  colloidal  solution.  On  allowing  these  red  solutions  to  stand  for  some 
time,  black  nickel  suboxide  separates  out  in  a  flocculent  mass.  Oils  in  addition 
to  water  have  the  power  of  taking  up  the  suboxide  in  a  colloidal  form. 

On  heating  nickel  suboxide,  prepared  according  to  one  of  the  methods  de- 
scribed in  literature,  with  a  fat  or  fatty  acid,  the  nickel  suboxide  distributes 

*  Drugs,  Oils  and  Paints,  1914,  211. 

f  Japanese  Patent  31,590,  October  4,  1917;  Chem.  Abs.,  1918,  538. 
$  Poggendorf's  Annalen,  136,  1869,  51. 
§  Zeitschrift  fur  anorg.  Chemie,  36,  18. 
II  Chemical  News,  71,  1895,  81. 


THE  BASE  METALS  AS  CATALYZERS  209 

itself  therein  in  an  exceedingly  fine  state  of  division  to  form  a  black,  inky 
liquid  which  passes  through  any  filter  unchanged.  The  same  colloidal  division 
takes  place  if  a  higher  nickel  oxide  be  suspended  in  a  fatty  oil  and  reduced  to 
nickel  suboxide  by  means  of  a  current  of  hydrogen.  This  property  of  colloidal 
distribution  imparts  to  the  nickel  suboxide  to  an  extreme  degree  the  power  of 
adding  hydrogen  to  unsaturated  fatty  acids  and  their  glycerides  in  a  manner 
similar  to  that  in  which  the  addition  of  hydrogen  takes  place  by  means  of  col- 
loidal platinum. 

In  operating  the  process  of  British  Patent  No.  26,912,  of  1910,  nickel  suboxide 
is  stated  to  be  formed  to  a  certain  extent  when  ordinary  nickel  oxide  is  em- 
ployed in  the  process  of  hydrogenation.  In  the  present  case,  however,  nickel 
suboxide  is  first  prepared  and  is  then  added  to  a  quantity  of  the  oil  which  is  to 
be  hydrogenated.  The  advantage  derived  by  this  procedure  resides  in  the  lower 
temperature  at  which  the  addition  of  hydrogen  takes  place.  Thus,  it  is  not 
necessary  to  heat  the  oil  so  strongly  as  when  ordinary  nickel  oxides  are  employed. 

(A)  Sesame  oil  is  heated  in  a  copper  vessel  with  1  per  cent  of  nickel  sub- 
oxide  to  200°  C.,  and  a  strong  current  of  hydrogen  is  passed  through  the  oil. 
The  suboxide  immediately  forms  with  the  oil  an  inky  liquid  and  after  a  few 
hours  the  mass  solidifies  at  46°  C. 

(B)  Ordinary  nickel  oxide  in  as  finely-divided  condition  as  possible  is  heated 
with  ten  times  its  weight  of  cotton  oil  to  260°  C.,  and  a  strong  current  of  hydro- 
gen passed  through  for  one  hour  whereupon  the  greyish  green  oxide  assumes  a 
black  color  and  distributes  itself   colloidally  throughout  the   oil.     The  mass  is 
allowed  to  cool  somewhat  and  then  run  into  200  times  its  weight  of  cotton  oil 
which  is  now  hydrogenized  at  185°  C.     After  two  hours  the  solidifying  point  of 
the  mass  is  about  50°  C. 

In  the  prosecution  of  the  application  from  which  U.  S.  Patent  No.  1,026,339, 
of  May  14,  1912,  to  Bedford  and  Williams  was  derived,  the  statement  appears 
that: 

It  has  never  been  known  to  hydrogenize  unsaturated  compounds  with  nickel 
oxide  as  a  catalyzer  at  any  other  than  very  high  pressures  which  render  the 
processes  unworkable  as  commercial  processes  as  is  evidenced  by  the  following 
literal  translation  of  a  portion  of  a  paper  contributed  by  S.  Fokin  in  the  Journal  of 
the  Russian  Chemical  Society,  1910,  page  1074. 

"  It  has  been  found  by  V.  I.  Ipatiew  that  Ni2O3,  when  used  for  experiments  at 
high  temperatures  and  pressures,  gives,  as  regards  the  velocity  of  the  reaction 
of  the  hydrogenization  of  unsaturated  compounds,  a  better  effect  than  metallic 
nickel  reduced  from  its  oxide.*  The  participation  of  some  of  the  lower  forms 
of  nickel  oxide  appeared  to  be  very  probable  and  to  explain  this  unexpected 
circumstance.  But  if  such  explanation  is  suitable  for  very  high  pressures  noth- 
ing similar  is  observed  at  pressures  within  the  limits  of  ten  to  twenty  atmos- 
pheres and  at  ordinary  pressure.  The  nickel  oxide  becomes  reduced  to  suboxide 
and  there  the  matter  ends.  The  hydrogenization  of  the  unsaturated  com- 
pounds does  not  take  place  here." 

What  is  termed  a  semi-reduced  hydrogenation  catalyzer  is  detailed 
by  Ellis, f  the  preparation  of  which  is  carried  out  by  the  careful 

*  Method  of  Sabatier  &  Senderens. 

t  U.  S.  Patent  No.  1,159,480,  November  9,  1915. 


210  THE  HYDROGENATION  OF  OILS 

reduction  of  nickel  oxide  or  hydrate  to  effect  only  partial  reduction, 
ordinarily  about  one-half  of  the  oxygen  being  removed,  affording  an 
intimate  mixture  of  catalytic  nickel  combined  with  nickel  oxide  or 
certain  of  the  suboxides.  Besides  hydrogen,  other  reducing  gases  or 
vapors,  namely,  water  gas,  carbon  monoxide  and  the  vapor  of  alco- 
hol, are  mentioned. 

A  catalytically  active  nickel  black  is  produced  by  Boyce  *  by  reducing 
nickel  oxide  with  hydrogen.  The  action  is  stopped  before  complete 
reduction  takes  place,  leaving  a  product  which  is  predominately  black. 

Boehringer  &  Sohne  f  hydrogenate  unsaturated  substances  in  the 
presence  of  a  suboxide  of  the  nickel  group  as  catalyst.  The  sub- 
stances are  treated  when  in  solution  or  suspension  in  an  alcohol 
instead  of  in  water.  {  In  examples,  dihydroquinine  is  obtained  by 
treating  quinine  hydrochloride  in  solution  in  methyl  or  ethyl  alcohol 
in  the  presence  of  nickel  suboxide,  and  cinnamylcocaine  is  hydro- 
genated  when  in  solution  in  ethyl  alcohol  in  the  presence  of  the 
same  suboxide. 

Meigen  §  defends  his  former  assertion  that  it  is  metallic  nickel 
which  transfers  hydrogen  to  oils  and  fats  instead  of  some  suboxide 
of  nickel  as  maintained  by  Erdmann  and  Bedford.  || 

New  experiments  are  described,  some  in  detail,  on  the  hardening  of  sesame 
and  soya-bean  oils  at  240°  to  280°,  using  nickel  oxides  and  at  170°  to  180° 
using  reduced  nickel  as  catalyzers.  Results  of  tests  for  metallic  nickel,  evolution 
of  hydrogen,  electrical  conductivity  and  formation  of  nickel  carbonyl  are  given. 
Summary:  (1)  nickel  oxide  is  an  active  catalyst  only  when  free  metal  is  present. 
(2)  Erdmann's  objections  to  Meigen's  former  experiments  are  based  on  false 
assumptions.  (3)  The  presence  of  free  metal  in  used  catalyzers  is  again  proved. 
(4)  Lack  of  electrical  conductivity  or  absence  of  the  carbonyl-reaction  are  not 
proof  of  the  absence  of  free  nickel,  while  positive  results  with  these  tests  always 
prove  its  presence.  (5)  The  specific  gravity  of  catalyzers  depends  essentially 
upon  organic  impurities  and  proves  nothing  as  regards  presence  of  nickel  sub- 
oxide.  (6)  The  assertion  that  suboxide  or  "  suboxide  hydride  "  is  formed,  is  not 
proved. 

The  principal  results  of  an  investigation  made  by  Frerichs  If  are 
summarized  as  follows: 

It  is  solely  an  assumption  of  Erdmann  and  his  co-workers  that  reduction  of 
nickel  oxides  in  oil  by  means  of  hydrogen  stops  with  the  formation  of  a  sub- 
oxide  and  that  such  suboxide  acts  as  a  hydrogen  carrier.  The  existence  of  a 
nickel  suboxide  is  held  to  be  entirely  problematical.  Equally  questionable  are 

*  Canadian  Patent  No.  171,436,  Aug.  22,  1916;  Chem.  Aba.,  1918,  749. 

t  British  Patent  No.  21,948,  November  3,  1914;  Chem.  Aba.,  1916,  1407. 

j  See  British  Patent  No.  21,883,  1914;  Chem.  Aba.,  10,  1081. 

§  J.  prakt.  Chem.,  92,  390-411,  1915;  Chem.  Abs.,  1916,  1105. 

||  Chem.  Abs.,  9,  3136. 

f  Arch.  Pharm.  253,  512,  1915;  Chem.  Abs.,  10,  1441. 


THE  BASE  METALS  AS  CATALYZERS  211 

assumptions  and  assertions  that  hydrated  nickel  oxides  are  formed,  or  that  nickel 
compounds  in  general  can  act  as  hydrogen  carriers.  It  has  been  demonstrated 
with  certainty,  not  only  through  electrical  conductivity  but  also  with  the  car- 
bonyl  test,  that  metallic  nickel  results  during  the  hardening  of  fats  through 
application  of  nickel  and  other  nickel  compounds.  Thus  it  has  been  shown  that 
reduction  of  nickel  oxide  in  oil  by  hydrogen  does  not  stop  at  a  suboxide  but  on 
the  contrary  progresses  as  in  an  ordinary  dry  reduction  to  the  metal  itself.  It 
is  certain  that  the  inability  on  the  part  of  Erdmann  and  co-workers  to  detect 
metallic  nickel  by  means  of  electrical  conductivity  was  in  the  main  due  to  con- 
taminations of  fatty  acid  salts  of  nickel  and  other  products  contained  in  the 
samples  examined.  Thus,  Siegmund  and  Suida  failed  to  detect  electrically  a 
content  of  at  least  48  per  cent  nickel  which  according  to  their  own  analyses 
must  have  been  present.  Erdmann's  explanation  of  the  action  of  nickel  oxides 
as  given  in  a  series  of  tests  designed  to  be  comparative  cannot  be  regarded  as  a 
proof,  since  possibility  for  comparison  is  excluded  under  the  varied  conditions 
obtaining  in  metallic  nickel  reduced  in  oil  and  in  the  dry  state.  Frerichs  further 
asserts  that  it  must  be  regarded  as  proved  that,  in  hardening  fat  by  use  of  nickel 
oxide,  the  hydrogen  carrier  is  in  reality  metallic  nickel  freed  from  its  compounds  by 
the  cation  of  hydrogen.  The  statement:  "  No  hardening  of  fat  without  free 
metal  "  he  believes  is  justified  in  view  of  the  present  state  of  the  science  and  the 
exact  experimentation  which  has  been  accomplished. 

As  a  proof  that  the  lack  of  electrical  conductivity  does  not  neces- 
sarily indicate  the  absence  of  metallic  nickel  Normann  *  cites  an 
experiment  in  which  a  contact  material  prepared  from  purified 
kieselguhr  with  about  20  per  cent  of  nickel,  reduced  for  an  hour  at 
500°  C.  in  hydrogen,  showed  no  conductivity.  On  the  other  hand, 
the  same  kieselguhr  mixed  with  5  per  cent  of  nickel,  prepared  by  the 
reduction  of  nickel  oxide  at  280°  C.,  showed  pronounced  conductivity. 

In  answer  to  Erdmann's  assertion  that  the  reduction  of  nickel  oxide  during 
hydrogenation  was  due  to  impurities  in  the  oil,  Normann  describes  an  experi- 
ment in  which  100  g.  of  synthetic  triolein  was  mixed  with  1  g.  of  pure  nickel 
oxide  and  hydrogenated  at  250°  C.  Within  a  few  minutes  a  pronounced  carbon yl 
reaction  was  obtained,  and  the  mixture  was  strongly  electrically  conductive. 
Notwithstanding  Erdmann's  hypothetical  assertions,  Normann  repeats  his  con- 
clusion that  without  free  metal  there  can  be  no  hydrogenation  of  fats.f 

By  the  process  of  Lever  Bros.  J  hydrogenation  is  effected,  while  the  fats  em- 
ployed are  maintained  in  the  liquid  state,  in  the  presence  of  catalyzers  which 
are  substantially  suboxides  of  metals,  especially  nickel.' 

The  results  of  the  studies  of  Erdmann  and  Bedford  §  on  the  cata- 
lytic action  of  nickel  oxides  has  been  criticized  by  Meigen  and  Bar- 
tels  (see  page  128),  who  have  made  the  assertion,  before  the  Natural 
Science  Society  in  Freiburg-in-Breisgau  ||  and  later  published  the 

*  J.  S.  C.  I.,  1916,  641;  Chem.  Ztg.,  1916,  40,  381-383. 

t  J.  S.  C.  I.,  1915,  237,  969;  1916,  262. 

t  Swedish  Patent  No.  40,305,  March  8,  1916;   Chem.  Abs.,  1916,  1603. 

§  J.  prakt.  Chem.,  1913  (2)  87,  425. 

[|  Report  of  the  Natl.  Sci.  Soc.  in  Freiburg  for  the  session  of  July  17,  1913. 


212  THE  HYDROGENATION  OF  OILS 

statement  *  that  nickel  oxides  yield  bodies  active  as  hydrogenating 
catalysts,  only  when  reduction  to  the  metallic  state  has  taken  place. 
Meigen  and  Bartels  further  asserted  that  the  opinion  brought  for- 
ward by  Erdmann  and  Bedford  that  a  suboxide  is  formed  during 
the  reduction,  is  not  confirmed. 

In  a  paper  of  considerable  length  f  Erdmann  endeavors  to  disprove  the  con- 
clusions of  Meigen  and  Bartels.  He  first  reviews  the  historical  side  of  the  hydro- 
genation  prior  to  the  work  of  Sabatier  and  Senderens.  An  impetus  was  given 
to  the  problem  of  oil  hardening  by  the  well-known  work  of  Sabatier  and  Sen- 
derens, who  recognized  that  finely-divided  metallic  nickel  and  several  allied 
metals  are  active  hydrogen  conveyors.  Erdmann  regards  the  application  of 
their  method  for  fatty  substances  was  natural,  although  not  included  within  the 
range  of  their  experiments.  In  1902  the  Herford  Oil  Works,  Leprince  and 
Siveke  (page  9)  applied  for  a  German  patent  based  on  Normann's  experi- 
ments, and  Normann  himself  applied  for  an  English  patent  for  the  conversion 
of  unsaturated  fatty  acids  or  their  glycerides  into  saturated  compounds,  em- 
ploying as  a  catalyzer  finely-divided  metals,  particularly  nickel.  According  to 
this  patent  specification,  Normann  makes  use  of  the  process  of  Sabatier  and 
Senderens  of  the  passing  of  vapors  over  a  contact  metal,  and  also  Saytzcff's 
process  of  mixing  the  contact  substance  with  the  liquid  for  the  particular  case 
of  the  hydrogenation  of  unsaturated  fatty  substances.  Erdmann  has  been 
informed  by  the  applicants  for  the  German  patent,  that  the  specification  was 
written  on  the  strength  of  some  test-tube  experiments.  The  patent  was  granted 
in  1903  t  and  such  rights  at  least  for  six  years  existed  on  paper  only,  without 
being  carried  out  on  a  large  scale.  In  1908  the  Herford  Oil  Works  operated 
an  experimental  plant  for  hardening  fats,  but  abandoned  it,  as  the  process  was 
too  incomplete  and  the  product  obtained  was  not  entirely  satisfactory.  In  1908 
this  firm  sold  its  British  and  in  1910  its  German  patents  to  Crosfield  &  Sons 
in  Warrington.  In  the  factory  of  this  English  firm  the  catalytic  process  was 
developed,  particularly  by  the  work  of  Kayser.  In  1911  the  Dutch  firm,  Naam- 
looze  Vernootschap  Ant.  Jurgens  Vereenigde  Fabrieken,  acquired  a  license  for 
the  use  of  the  process  in  Germany  from  Crosfield  &  Sons,  and  founded  the 
Germania  Works  at  Emmerich-on-the-Rhine.  This  plant  was  put  into  opera- 
tion in  1912,  9£  years  after  the  application  for  the  German  patent. 

In  German  Patent  No.  266,438,  Erdmann  claims  that  he  and  his  associates 
were  the  first  to  ascertain  that  unsaturated  fats  may  be  more  easily  hydrogenated 
by  the  aid  of  finely-divided  nickel  oxide,  than  by  aid  of  the  metal.  At  the  time 
of  this  application,  that  is,  almost  seven  years  after  the  granting  of  the  German 
patent  for  the  nickel  process,  fatty  oils  were  nowhere  produced  on  a  factory 
scale  in  Germany.  When  Meigen  and  Bartels  state  that  merely  the  high  price  of 
technical  hydrogen  was  the  cause  of  the  delay  in  the  development  of  the  Nor- 
mann process,  Erdmann  thinks  it  shows  a  remarkable  lack  of  knowledge  of 
electrochemical  progress.  From  electrochemical  factories  as  early  even  as  1902, 
many  million  cubic  meters  of  hydrogen  were  allowed  to  escape  into  the  air, 

*  J.  prakt.  Chem.,  1914  (2)  89,  290. 

f  J.  prakt.  Chem.,  91,  469. 

J  German  Patent  No.  141,029;  British  Patent  No.  1515,  1903.  In  1908,  according 
to  Erdmann,  Normann  sold  his  rights  in  the  British  Patent  to  Leprince  and  Siveke 
for  £100. 


THE  BASE  METALS  AS  CATALYZERS 


because  no  use  was  known  for  it.  Thus,  as  early  as  1900,  Greisheim-Elektron 
had  available  in  Greisheim,  Bitterfeld  and  Rheinfelden  together  about  11,500 
H.P.  for  the  electrolysis  of  alkali  chlorides.  For  the  conditions  then  existing 
this  corresponds  to  an  annual  production  of  21,850  metric  tons  of  caustic  potash 
(or  16,100  metric  tons  of  caustic  soda)  accompanied  by  the  loss  of  about  4,500,- 
000  cubic  meters  of  hydrogen.  There  were  soon  added  the  great  works  of  the 
Badische  Co.,  with  8000  H.P.,  then  the  German  Solvay  Works,  the  Hoechst 
Dyestuff  Works  and  various  other  factories.  Erdmann  thinks  that  this  hydro- 
gen would  have  been  cheaply  furnished  for  the  hardening  of  oil,  if  the  process 
had  been  technically  ready. 

EXPERIMENTAL  WORK  BY  ERDMANN 

Hydrogenation  by  Means  of  Nickel  Oxide  and  Metallic  Nickel.  If  1  kilogram 
of  cottonseed  oil  is  heated  to  250°  C.  with  5  g.  of  nickel  oxide  produced  by 
moderate  ignition  of  nickel  nitrate,  while  passing  a  current  of  pure  hydrogen 
gas  at  the  rate  of  20  to  25  liters  per  minute  through  the  liquid,  after  one-half 
hour  the  liquid  becomes  black  like  ink.  After  two  or  three  hours,  if  the  mixture 
is  allowed  to  cool,  the  mass  solidifies  to  a  solid  in  which  the  catalyst  is  sus- 
pended. For  cottonseed  oil,  hydrogenation  takes  place  even  at  220°,  for  oleic 
acid,  at  180°  to  185°  C. 

A  comparative  experiment  made  with  5  g.  of  a  nickel  oxide,  reduced  by  Saba- 
tier's  method  at  280°  to  300°  C.  for  one  hour  in  a  current  of  hydrogen,  with 
repeated  agitation  and  the  reduced  material  added  to  preheated  cottonseed  oil 
(1  kg.)  on  treatment  with  hydrogen  in  the  same  way  as  in  the  first  experiment, 
affords  no  fine  division  of  the  nickel.  The  liquid  does  not  become  inky  black, 
and  on  shutting  off  the  current  of  hydrogen,  the  nickel  powder  settles  rapidly. 
Even  after  passing  in  hydrogen  for  many  hours,  the  oil  does  not  become  solid. 
With  2  per  cent  of  nickel  no  hydrogenation  takes  place,  unless  the  nickel  is 
converted  into  finest  state  of  subdivision  possible  by  special  methods. 

Two  experiments  with  linseed  oil  are  noted.  Nickel  oxide  used  in  both 
experiments,  was  of  a  voluminous  character  and  was  produced  by  the  process  of 
German  Patent  No.  260,009,  of  December  19,  1911,  by  allowing  a  concentrated 
nickel  nitrate  and  sugar  solution  to  drop  into  a  glowing  muffle.  This  catalyst 
is  referred  to  as  nickel  oxide  (vol.): 

(a)  Two  hundred  and  fifty  grams  of  the  linseed  oil  were  mixed  with  1.25  g. 
of  nickel  oxide  (vol.)  and  hydrogenated  at  255°  to  260°  C.  (6)  1.25  g.  nickel 
oxide,  (vol.)  were  reduced  for  one  hour  at  270°  C.,  then  added  to  250  g.  of  the 
linseed  oil  and  hydrogen  was  passed  through  for  several  hours  at  255°  to  260°  C. 


Time  in 

Tempera- 

SOLIDIFICATION POINT. 

Hours. 

ture. 

a 

b 

1 

260°  C. 

Beginning  of  hardening,  with 

Sample  remains  light 

ink-black  coloration. 

and  liquid. 

2 

240°  C. 

30.  7°  C. 

14 

3 

260°  C. 

40.  3°  C. 

" 

4 

253°  C. 

46.  5°  C. 

f| 

4' 

261°  C. 

47.  2°  C. 

* 

214 


THE  HYDROGENATION  OF  OILS 


The  conclusion  that  nickel  oxide  and  not  nickel  is  the  catalyst  he  considers 
is  reached  from  the  chemical  and  physical  examination  of  the  recovered  catalyst. 
This,  it  is  true,  is  complicated  by  the  fact,  that  it  is  not  possible  for  this  purpose 
to  remove  all  the  adhering  organic  substances.  The  recovery  may  be  carried 
out  by  allowing  the  oil  and  catalyzer  to  settle  for  a  day  at  60°  C.  After  cooling, 
the  lower  black  layer  of  the  cake  is  separated  from  the  light-colored  fat  and  is 
placed  in  a  Soxhlet  extraction  thimble.  It  is  then  extracted  for  twenty  hours 
with  boiling  benzol,  and  dried  in  a  vacuum.  The  residue  is  placed  in  a  fresh 
thimble  and  again  extracted  for  twenty  hours  with  benzol.  In  this  way  it  is 
possible  to  recover  a  catalyst  which  does  not  contain  more  than  a  maximum 
of  3.5  per  cent  of  carbon.  The  coal-black  powder  thus  obtained  has  reducing 
properties.  It  liberates  nitric  oxide  from  nitric  acid  and  hydrogen  from  dilute 
sulphuric  acid.  It  colors  aqueous  solutions  of  phosphotungstic  acid  and  phos- 
phomolybdic  acid  blue,  and  in  this  respect  does  not  behave  differently  than 
finely-divided  nickel.  The  degree  of  reduction  of  this  substance  (which  is  meas- 
ured by  the  hydrogen  developed),  does  not  continuously  increase  with  the 
length  of  time  it  is  used  as  a  catalyst.  Erdmann  has  given  two  methods  by 
which  nickel  and  nickel  suboxide  may  be  differentiated,  namely:  by  the  deter- 
mination of  the  electric  conductivity  and  by  the  carbonyl  reaction.  By  the  aid 
of  these  two  methods,  he  determined  that  no  metallic  nickel  could  be  detected 
in  the  recovered  catalyst,  and  that  the  reducing  properties  must,  therefore,  be 
considered  as  being  due  to  a  lower  oxide  of  nickel. 

For  the  hydrogenation  experiments  of  the  table  following,  cottonseed  oil 
purified  in  Erdmann's  laboratory,  trioleine  found  by  analysis  to  be  pure,  and 
the  purest  oleic  acid  from  Merck,  were  used. 

(a)  COTTONSEED  OIL  PURIFIED  BY  STEAM 


No. 

Amount 
of  Cata- 

Temp. °  C. 

Time, 

Solidification. 

Con- 
duc- 

Remarks. 

lyst  Gm. 

Hrs. 

tivity 

1 

j 

210-220 

3 

57.2 

0 

No  carbonyl  reaction 

2 

5 

225 

II 

27.8 

0 

Ni  =74.3%  i,  H  =  102  cc.  * 

3 

8 

f       255 
t       218 

2* 

}                     42 

0 

4 

7 

235-238 

34 

40 

0 

5 

7 

240-243 

21 

39.5 

0 

6 

5 

250-255 

2* 

45 

0 

Extraction  in  COa  current 

7 

8 

240-244 

5 

33.5 

0 

8 

8 

/       250 
\      230 

1 
11 

\                                      00     Q 

/                      32'3 

0 

9 

8 

f       250 
\  230-240 

1 
11 

j                    37.7 

0 

Extraction  in  COa  current 

10 

11 

239-243 

3J 

43.5 

0 

11 

11 

240-245 

21 

30 

0 

21C-220 

210-220 

255 


(b)  SYNTHETIC  TRIOLEIN 

22.5 

28 

Solid  but  solidification  point 
not  determined 

(c)  OLEIC  ACID  (MERCK) 


No  carbonyl  reaction 
No  carbonyl  reaction 
Extraction  in  CO2  current 


15 

1 

220-225 

3 

55.6 

0 

Ni=74.4%',H=80.7cc.2 

16 

1 

200 

6 

57.3 

0 

C=3.58%  H=0.95% 

17 

1 

180-185 

8 

56 

0 

Ni=76.9%  i  H=81.9  cc. 

1  Ni  content  of  the  recovered  catalyst. 

2  This  figure  relates  to  the  amount  of  hydrogen  (reduced  to  0°  C.  at  760  mm.)  produced  from 
1  g.  of  the  recovered  catalyst  when  treated  with  EhSCh. 

In  Nos.  1,  2,  3,  4,  5,  6,  12,  13,  14,  15,  16  and  17  voluminous  nickel  oxide  was  used.      In  NOB.  7, 
8  and  9  Kahlbaum's  nickel  oxide  and  in  Nos.  10  and  11  nickel  hydrate  was  used. 


THE  BASE  METALS  AS  CATALYZERS 


215 


CATALYZER,  ONE  PER  CENT  OF  NICKEL  OXIDE  (VOLUMINOUS) 


2 

§ 

j£ 

I 

No. 

Oil. 

Temp.,  °  C. 

j 

Remarka. 

I 

il 

H 

i 

o 

18 

Refined  cottonseed  oil  .... 

230-246 

3 

39 

+ 

19 

Edible  cottonseed  oil  

260 

1 

39.2 

-f 

20 

Pure  cottonseed   oil   hard- 

260 

6 

.  . 

+ 

Catalyst  flocculated 

ened  to  57° 

out 

21 

Hardened  linseed  oil  

260 

6 

+ 

Catalyst  flocculated 

out.     H  =  294cc. 

22 

Pure   cottonseed  oil  hard- 

195-200 

51 

0 

No  flocculation 

ened  to  57.5°  C.1 

23 

Linseed  oil             .    .    . 

f    260 

1    | 

52.7 

o 

No  flocculation 

I    200 

8^  / 

24 

Oleic  acid  (Merck)  

/    250 
I    200 

LI 

63 

0} 

Ni  =  75.2  per  cent 
H  =104cc. 

1  The  catalyst  had  already  been  used  once  and  recovered. 

Erdmann  considers  the  solidification  point  of  more  significance  than  the  iodine 
number,  as  the  latter  may  be  misleading,  when  polymerization  has  taken  place. 
Linseed  oil  (Test  23)  was  hydrogenated  for  one  hour  at  260°  C.  then  for  8| 
hours  at  200°  C.  After  three  hours  the  solidification  point  was  46.2°  and  did 
not  increase  with  further  treatment.  Nevertheless  the  catalyst  remained  well 
divided  and  did  not  flocculate  out.  Nickel  formation  did  not  set  in  at  200°  C. 
Oleic  acid  (Test  24)  treated  with  hydrogen  at  200°  C.  gave  after  nine  hours  a 
solidification  point  of  63°,  which  did  not  increase  in  several  hours  subsequent 
treatment.  Nickel  likewise  was  not  formed.  The  conditions  are  favorable  for 
formation  of  nickel,  when  a  high  temperature  (260°  C.)  and  a  large  quantity  of 
catalyst  are  used  with  an  oil  such  as  cottonseed  oil,  which  readily  takes  up 
hydrogen.  The  hydrogenation  then  becomes  so  vigorous  that  the  temperature 
in  the  interior  may  be  raised  by  the  heat  of  reaction  above  that  of  the  oil  bath 
used  for  heating  purposes.  This  spontaneous  heating,  it  is  stated,  favors  reduc- 
tion to  the  metallic  state.  For  cottonseed  oil  0.5  per  cent  or  at  most  1  per  cent 
nickel  oxide  (vol.)  suffices  perfectly  for  the  hydrogenation. 

According  to  Erdmann 's  analyses  the  amount  of  hydrogen  developed  by  a 
recovered  catalyst  when  treated  with  sulphuric  acid  never  reached  the  amount 
of  233  cc.  from  1  g.  of  substance,  which  would  be  the  amount  expected  from  a 
pure  compound  having  the  formula  Ni3O.  The  amount  of  hydrogen  given  off  is 
usually  not  even  half  as  large  as  that  (see  tests  2,  15,  17  and  24  in  the  above 
tables)  and  only  exceeds  it  when  nickel  was  produced  deliberately  and  was 
detectable  by  the  conductivity  (Test  21).  Meigen  and  Bartels  contend  that  they 
are  able  to  refute  Erdmann's  statements  by  two  analyses.  (1)  0.1488  g.  of 
catalyst  produced  43.1  cc.  of  hydrogen  (reduced  to  0°  at  760  mm.)  and  0.1316  g. 
nickel  (corresponding  to  88.4  per  cent).  (2)  0.0976  g.  of  catalyst  gave  22.6  cc. 
of  hydrogen  (reduced)  and  0.0725  g.  of  nickel  (corresponding  to  74.6  per  cent). 

Contrary  to  the  statements  of  these  writers,  the  nickel  content  does  not  in 


216  THE  HYDROGENATION  OF  OILS 

these  analyses  exceed  that  of  the  nickel  suboxide,  Ni3O,  as  this  amounts  to  91.7 
per  cent.  When  Erdmann  calculated  these  analytical  results  for  nickel  suboxide 
(Ni3O)  he  obtained  from  the  first  analysis  the  figure  140.4  per  cent  and  in  the 
second  134.3  per  cent,  which,  of  course,  is  impossible.  Erdmann  notes  that,  in 
some  cases  a  part  of  the  hydrogen  generated  by  the  action  of  acids  may  be  due 
to  the  formation  of  hydride.  Hydrided  nickel  oxides  of  the  following  forms  are 
conceivable:  (1)  H— Ni  (OH);  (2)  H— Ni— O— Ni  (OH);  (3)  H—  Ni— O— Ni— H 
and  others.  Such  hydrides  would  necessarily  produce  more  hydrogen  with  acids 
than  a  suboxide  (NisO).  The  assumption  that  perhaps  a  mixture  of  such  nickel 
oxide  hydrides  are  present  in  the  catalyst  used  for  the  hydrogenation  is  not  a 
purely  speculative  one,  but  is  corroborated  by  an  examination  of  the  recovered 
catalyst.  If  the  latter,  after  drying  in  a  current  of  neutral  gas  or  in  a  vacuum 
is  heated  to  250°  C.  steam,  in  addition  to  small  amounts  of  hydrogen,  is  found 
to  be  given  off.  The  catalyst,  thus  heated,  sometimes  shows  electric  conductivity, 
i.e.,  the  heating  has  produced  nickel.  In  other  cases,  usually  when  the  hardening 
has  not  been  carried  far,  no  nickel  can  be  detected  after  the  heating. 

Electric  Resistance.  Tubandt,  director  of  the  physico-chemical  department 
of  the  University  Institute  in  Halle  made  some  measurements  of  resistance  with 
used  nickel  oxide  catalysts,  for  Erdmann. 

Preparation  of  Catalyzers.  (1)  Linseed  oil  with  1  per  cent  of  nickel  oxide 
(vol.)  was  hardened  for  three  hours.  Solidification  point  42°  C.  Hardening 
temperature  260°  C.  (one  hour)  and  210°  C.  (two  hours).  (2)  Edible  cotton- 
seed oil,  purified  by  distillation  with  steam,  was  hardened  with  1  per  cent  of 
nickel  oxide  (vol.)  for  2£  hours  at  250°  to  255°  Solidification  point  44°  C. 

These  catalyzers  were  pressed  into  tablets  of  10  mm.  diameter  and  2  to  5  mm. 
height  by  means  of  a  pressure  of  1000  atmospheres  in  a  steel  cylinder.  Plat- 
inum discs  with  welded  platinum  wires  were  pressed  against  the  flat  end  sur- 
faces of  the  tablets.  In  order  to  insure  a  contact  with  the  platinum  discs  as 
free  of  induction  resistance  as  possible,  the  ends  of  the  tablets  were  gold  plated. 
The  conductivity  measurements  were  made  with  a  Wheatstone  bridge  provided 
with  alternating  current  and  a  telephone  receiver.  The  apparatus  permitted 
the  measurement  of  resistances  of  several  millions  of  ohms  with  certainty. 
Tubandt  made  measurements  of  the  conductivity  at  different  temperatures  from 
room  temperature  up  to  300°  C. 

Catalyst  (1)  at  16°  afforded  a  specific  resistance  of  3,000,000  ohms,  at  150°, 
1,600,000  ohms,  at  200°,  after  heating  for  one  hour,  376,400  ohms  and  after 
cooling  to  16°,  300,000  ohms.  After  heating  for  two  hours  up  to  300°  the  fol- 
lowing measurements  were  taken  at  300°  C.,  196.4  ohms  and  after  cooling  to 
15°  C.  78,560  ohms.  The  catalyst,  therefore,  first  shows  the  typical  behavior  of 
a  poorly  conducting  metal  oxide.  It  conducts  decidedly  more  poorly  than  pure 
nickel  oxide,  for  which  at  17°  a  specific  resistance  of  10,720  ohms  was  deter- 
mined. A  difference  is  shown  by  the  decrease  in  resistance  at  higher  tempera- 
tures, finally  reaching  an  almost  constant  point  (when  the  temperature  remains 
unchanged).  Erdmann  offers  the  surmise  that  an  explanation  may  be  found  in 
the  fact  that  at  the  higher  temperature  a  part  of  the  suboxide  is  reduced  to 
metallic  nickel  by  the  occluded  hydrogen. 

Catalyst  (2)  at  170°  exhibited  a  specific  resistance  of  3,000,000  ohms,  and  at 
61°  C.  the  resistance  was  2,266,000  ohms.  On  further  slow  heating  the  resistance 
slowly  decreases  with  the  rising  temperature.  At  270°  this  decrease  is  very 
rapid.  At  290°  the  resistance  became  0.207  ohm  and  at  16°  the  figure  obtained 


THE  BASE  METALS  AS  CATALYZERS  217 

was  9.1524  ohms.  The  'phenomena  are  analogous  to  those  observed  in  (1), 
except  that  on  heating,  so  much  nickel  is  formed  that  the  substance  becomes 
readily  conductive.  The  temperature  coefficient  of  conductivity  before  heating 
is  positive — the  suboxide  being  an  electrolytic  conductor  of  the  current — and, 
after  heating,  the  coefficient  is  negative  (metallic  conduction). 

Erdmann  concludes  that  all  these  measurements  indicate  the  used  nickel 
oxide  catalyst  not  to  contain  metallic  nickel,  at  least  not  in  appreciable  quanti- 
ties. When  nickel  is  actually  present,  either  added  to  the  catalyst  at  the  start, 
or  formed  by  the  occluded  hydrogen  on  heating  the  oil-free  catalyst,  it  can  be 
detected  by  measuring  the  electric  conductivity. 

Erdmann  made  various  observations  by  means  of  the  nickel  carbonyl  reaction 
to  prove  the  presence  or  absence  of  nickel.  Experiments  were  carried  out  as 
follows:  50  to  100  g.  of  the  oil  were  heated  with  the  addition  of  1  to  2  per  cent 
of  nickel  oxide  (vol.)  in  a  flask  (only  vessels  of  glass  can  be  used),  with  bottom 
tube,  and  the  oil  hydrogenated  to  a  solidification  point  of  28°  to  33°  C.  The 
glass  flask  was  then  heated  in  a  water-bath  at  30°  to  35°  C.  Hydrogen  was 
replaced  by  pure  dry  carbon  monoxide  which  was  led  into  the  flask  by  means 
of  a  T  tube  from  a  gasometer.  Thus,  there  was  no  necessity  of  transferring 
and  exposing  hardened  fat  during  the  test.  For  a  period  of  fifteen  to  thirty 
minutes  no  nickel  mirror  was  formed  on  heating  the  escaping  gas  passing  through 
a  glass  tube  used  for  the  mirror  test.  A  colloidal  solution  of  metallic  nickel  in 
oil,  obtained  by  electric  atomizing  of  reduced  nickel  into  linseed  oil,  was  tested 
in  the  same  way;  50  cc.  of  the  colloidal  solution,  whose  nickel  content  was 
0.046  g.,  were  placed  in  the  flask.  A  nickel  mirror  was  at  once  obtained.  A 
nickel  mirror  was  obtained  within  three  minutes  when  carbon  monoxide  was 
passed  over  dry  metallic  nickel  at  34°  C.  which  had  been  obtained  by  reducing 
0.13  g.  nickel  oxide  (vol.)  with  hydrogen. 

By  these  tests,  Erdmann  considers  it  is  proven,  even  when  only  small  amounts 
of  nickel  are  present,  that  a  temperature  of  about  30°  C.  is  actually  sufficient 
for  the  formation  of  the  nickel  carbonyl.  If  at  30°  C.  during  the  course  of 
fifteen  minutes  no  mirror  is  produced  by  carbon  monoxide,  Erdmann  states  this 
proves  the  absence  of  metallic  nickel. 

The  following  experiments  also  were  made: 

One  hundred  cc.  cottonseed  oil  were  hardened  with  the  addition  of  1  g. 
nickel  oxide  (vol.)  for  |  hour  at  250°  to  255°  C.  The  ink-like  liquid  was  then 
treated  at  50°  with  dry  carbon  monoxide  in  the  same  flask.  The  escaping  gas 
flowed  through  a  heated  glass  tube  and  then  was  ignited.  In  the  first  ten  min- 
utes no  mirror  was  formed,  nor  were  any  dark  spots  formed  on  a  piece  of  por- 
celain when  held  over  the  flame.  After  seventeen  minutes  such  spots  were 
formed  and  a  nickel  mirror  appeared.  After  thirty  minutes  the  mirror  was 
heavy,  the  carbon  monoxide  flame  had  an  internal  cone  with  a  luminous  point 
and  readily  deposited  nickel  spots  on  porcelain.  The  experiment  was  repeated 
at  60°,  at  70°  to  75°  and  at  80°  to  85°.  Highly  hardened  cottonseed  oil  was 
also  used,  but  without  producing  any  change  in  the  result.  A  certain  period  of 
time  always  elapses  before  a  deposition  of  nickel  becomes  noticeable.  However, 
it  is  easy  to  overestimate  the  amounts  of  nickel  deposited.  The  weight  of  the 
heavy-appearing  nickel  mirror  deposited  during  half  an  hour  at  50°  in  the  above 
experiment  amounted  only  to  a  few  tenths  of  a  milligram.  A  second  experiment 
at  70°  to  75°  for  a  full  hour  furnished  a  nickel  mirror  of  2.2  milligrams  and  a 
third  at  80°  to  85°  for  one  hour  a  mirror  weighing  2.7  milligrams. 


218  THE  HYDROGENATION  OF  OILS 

The  dependence  of  the  reaction  on  the  temperature,  and  its  almost  negative 
result  at  30°  point  to  a  reducing  action  by  the  carbon  monoxide. 

By  a  determination  of  the  amount  of  carbon  dioxide  formed,  it  is  proven 
that  at  80°  to  85°  C.  carbon  monoxide  has  a  reducing  action  on  the  nickel 
compounds  contained  in  the  hardened  fat. 

A  thesis  by  Agde  *  considers  the  subject  of  nickel  oxide  as  a  cata- 
lyzer, from  a  number  of  aspects.  In  order  to  study  the  question 
whether,  and  under  what  conditions  metallic  nickel  is  formed  during 
the  hydrogenation  of  fatty  substances  in  the  presence  of  nickel  oxides, 
it  appeared  necessary  to  use  as  raw  material  for  the  experiments, 
chemically  pure  substances,  or  at  least  natural  fatty  oils  purified  as 
far  as  possible.  Only  under  such  conditions  is  it  possible  to  exclude 
secondary  reactions.  Agde  has  therefore  mainly  used  chemically  pure 
oleic  acid,  synthetic  triolein  and  a  cottonseed  oil  carefully  freed  of 
aldehydes. 

If  voluminous  nickel  oxide  prepared  from  nickel  nitrate,  as  used  by  Agde 
in  most  of  the  experiments,  is  introduced  into  the  hot  oil  and  hydrogen  passed 
through  in  a  vigorous  current,  then  the  grey  color  of  the  catalyst  is  changed  to 
yellow-green.  It  then  spreads  through  the  oil,  more  or  less  rapidly,  depending 
on  the  temperature,  colors  the  oil  grey  and  finally  black.  This  last  change  of 
color  into  grey  to  black  is  an  indication  of  the  commencement  of  the  hardening 
of  the  oil.  With  the  glycerides  this  distribution  takes  place  more  rapidly  and 
completely  than  with  the  free  fatty  acid.  Agde  has  also  determined  that  with 
the  glycerides  colloidal  transfusion  or  distribution  occurs.  When  the  black 
liquid  is  treated  with  benzol,  then  filtered  through  hardened  filter  paper,  clear 
deep  brown  filtrates  were  obtained  which  were  examined  under  the  ultramicro- 
scope.  The  filtrate  from  synthetic  triolein  showed  mainly  amicrons  and  that 
from  cottonseed  oil  only  submicrons. 

A  nickel  oxide  catalyst  used  for  a  second  time,  distributes  in  the  oil  at  once, 
thereby  shortening  the  time  for  the  hardening.  The  catalyst  cannot  be  used 
as  often  with  oleic  acid  as  with  a  glyceride.  The  frequency  of  this  re-use  nat- 
urally also  depends  upon  the  original  amount  of  the  catalyst.  With  2  per  cent 
of  catalytic  substance  successive  portions  of  oleic  acid  could  be  highly  hardened 
three  times.  With  1  percent  of  catalytic  substance  the  nickel  oxide  was  floc- 
culated out  when  used  a  third  time — a  sign  that  its  activity  was  ceasing  and 
with  %  per  cent  of  catalyzer  this  flocculation  took  place  during  the  second  hard- 
ening of  the  oleic  acid. 

The  required  initial  temperature  varies  for  different  oils.  For  oleic  acid  it  is 
comparatively  low,  Agde  determined  it  as  being  180°  to  185°  C.  But  at  such  a 
low  temperature  the  hardening  takes  place  slowly.  Over  seven  hours  duration 
were  necessary  to  reach  a  solidification  point  of  56°,  while  the  same  result  was 
obtained  in  three  hours  at  225°  C.  This  is  in  part  caused  by  the  fact  that  the  first 
phase,  the  distribution  stage,  requires  a  long  time.  The  course  of  the  hardening 
of  oleic  acid  was  ascertained  for  the  temperatures  from  180°  to  250°  C.  For 
glycerides,  such  as  triolein,  cottonseed  oil  and  linseed  oil,  the  initial  temperature 

*  Halle,  1914,  under  Dr.  Erdmann. 


THE  BASE  METALS  AS  CATALYZERS  219 

lies  beyond  200°  C.  (for  triolein  at  210°  to  220°  C.)  But  when  once  the  hydro- 
genation  has  started  the  temperature  can  be  lowered  for  its  further  progress. 
Agde,  therefore,  differentiates  between  initial  temperature  and  hardening  tem- 
perature. Oleic  acid  hardening  takes  place  at  100°  to  110°  if  it  has  once  been 
started. 

The  hardening  curves  up  to  a  certain  degree  rise  sharply  an  then  curve  more 
gradually.  The  commencement  of  the  gradual  curvature  is  dependent  on  the 
hardening  temperature  and  the  amount  of  the  catalytic  substance.  With  a  hard- 
ening temperature  of  250°  and  1  per  cent  of  catalytic  substance  this  curvature 
is  found  at  the  solidification  point  61°  for  oleic  acid;  for  triolein  it  is  at  about  45°. 

The  formation  of  nickel  aside  from  being  produced  by  the  aldehydic  impuri- 
ties already  mentioned  according  to  Agde  can  be  occasioned  only  by  overhardening. 
It  is  favored  by  a  high  hardening  temperature.  Although  the  catalyst  was  still 
free  of  nickel,  after  hardening  oleic  acid  for  4|  hours  at  250°  C.  to  solidification 
point  of  63°  the  metal  was  formed  after  hardening  for  6^  hours  at  255°  to  a 
solidification  point  of  64°.  Oleic  acid  could,  however,  be  hardened  at  200°  and 
treated  for  fifteen  hours  with  a  strong  current  of  hydrogen  (5  liters  per  minute) 
without  it  being  possible  to  detect  metallic  nickel  in  the  catalyst. 

In  general,  Agde  states,  with  faulty  carrying  out  of  the  hardening  operation 
or  with  poor  catalysts,  oleic  acid  will  give  occasion  for  the  formation  of  metallic 
nickel  more  readily  than  is  the  case  with  the  glycerides.  This  is  shown  by  an 
experiment  in  which  basic  nickel  carbonate  was  added  to  free  oleic  acid  at  ordi- 
nary temperature,  whereupon  it  was  warmed  very  slowly.  Under  these  condi- 
tions nickel  oleate  is  formed,  which  sets  nickel  free  at  a  high  temperature  under 
the  influence  of  hydrogen.  The  catalytic  action  is  thereby  destroyed;  for  the 
nickel  which  is  produced  in  this  way  is  in  the  form  of  metallic  scales  and  accord- 
ing to  Agde  has  as  little  power  to  transfer  hydrogen  as  has  the  reduced  nickel 
formed  by  over  hardening  the  oil. 

Preparations  of  nickel  oxide,  which — on  account  of  the  admixed  impurities 
which  they  contain  (for  instance,  too  high  an  alkali  content),  do  not  transfuse 
or  distribute  in  the  oleic  acid — may  also  be  reduced  to  nickel  accompanied  by  a 
loss  of  their  catalytic  activity.  In  the  apparatus  used,  a  flask  with  bottom  inlet 
tube,  this  is  favored  by  the  fact  that  the  nickel  oxide  is  precipitated  as  a  heavy 
deposit  in  the  bottom  tube,  while  the  oil  is  forced  out  of  the  tube  by  the  strong 
current  of  hydrogen,  thus  the  nickel  oxide  is  heated  directly  in  a  hydrogen 
atmosphere. 

The  criticism  that  metallic  nickel  loses  its  conductivity  by  being  acted  on  by 
the  oxygen  of  the  air  during  the  recovery  of  the  catalyst  is  also  refuted  by 
Agde,  who  filtered  and  extracted  the  catalyst  in  a  current  of  carbon  dioxide, 
but  the  results  were  the  same  as  those  from  the  experiments  made  without 
the  use  of  this  gaseous  atmosphere.  The  test  for  the  presence  of  metallic  nickel 
by  means  of  carbon  monoxide  is  also  negative  for  normal  hardening.  But  the 
temperature  during  the  action  of  the  carbon  monoxide  must  not  be  too  high,  as 
otherwise  nickel  oxide,  it  is  stated,  is  also  reduced  by  it  and  converted  into 
nickel  tetracarbonyl. 

In  a  number  of  cases  Agde  made  a  quantitative  analysis  of  the  used  nickel 
oxide  catalyst  which  had  been  carefully  decreased  by  means  of  benzol.  It  may 
be  noted  here  that  the  nickel  content  lay  between  75.2  per  cent  and  77.1  per 
cent,  the  carbon  content  between  2.9  per  cent  and  6.2  per  cent  and  the  hydrogen 
content  between  0.7  and  1.3  per  cent.  The  amount  of  hydrogen  produced  by 


220  THE  HYDROGENATION  OF  OILS 

acids  varied  between  80.7  and  108.6  cc.,  calculated  for  1  g.  of  catalyst,  while  1  g. 
of  a  nickel  suboxide,  Ni2O,  theoretically  yields  167.9  cc.  of  hydrogen  (1  g.  of  Ni3O 
can  furnish  233.1  cc.  of  hydrogen).  When  the  recovered  catalyst  has  been  used 
for  hardening  for  a  long  time  and  at  a  high  temperature,  it  develops  foul- 
smelling  gases  when  mineral  acids  are  poured  over  it.  These  gases  have  an  odor 
which  remind  one  of  the  odor  produced  when  iron  carbides  are  dissolved  in 
mineral  acids.  If  the  hardening  be  carried  out  at  low  temperatures,  or  f  it 
is  of  short  duration,  this  odor  cannot  be  perceived.  Furthermore  the  observa- 
tion was  made  that  the  recovered  catalyst  on  being  heated  over  200°  C.  develops 
hydrogen  and  at  250°  to  275°  C.  splits  off  water.  In  addition  small  amounts 
of  carbon  monoxide  were  also  set  free.  This  development  of  gas  and  steam  also 
takes  place  when  a  perfectly  anhydrous  nickel  oxide  and  a  carefully  dried  oil 
had  been  used  for  the  hardening. 

The  final  product  of  the  hardening  of  oleic  acid  is  a  stearic  acid  having  a 
melting-point  of  63°  which  corresponds  to  an  iodine  number  of  15.6.  With 
triolein,  however,  an  iodine  number  approximately  zero  is  attained.  The  saponi- 
fication  number  in  this  case  agrees  with  that  for  pure  tristearin  and  the  acid 
number  is  zero.  Therefore,  during  the  hardening,  nickel  oxide  does  not  produce 
any  sapanification. 

Agde  performed  some  experiments  with  several  other  organic  bodies,  in  addi- 
tion to  oleic  acid  and  fatty  oils,  in  order  to  determine  how  nickel  oxide  suspended 
in  these  substances  behaves  when  heated  during  the  passing  through  of  hydro- 
gen. With  paraffin  and  diphenylamine  there  resulted  a  rapid  reduction  to 
metallic  nickel.  In  paraffin  the  nickel  is  already  detectable  after  one-quarter  of 
an  hour,  and  after  one  hour  the  nickel  content  of  the  recovered  catalyst  amounts 
to  94.9  per  cent.  In  the  presence  of  beta-naphthol,  acetanilid,  anthracene  or 
phenathrene,  however,  there  is  also  a  reduction  of  the  nickel  oxide  but  after 
from  one  to  four  hours  treatment  with  hydrogen  at  250°  it  is  not  reduced  to 
the  metallic  state.  Evidently  the  last-named  substances  exert  a  protecting  influ- 
ence on  the  metallic  oxide.  No  connection  between  the  division  or  distribution 
of  the  nickel  oxide  and  the  viscosity  of  the  substances  could  be  proven. 

Agde  considers  his  studies  to  have  proven  beyond  all  doubt  that  in  the  oil- 
hardening  process  of  Bedford  and  Erdmann,  metallic  nickel  is  not  the  conveyor 
of  hydrogen.  He  claims  that  easily  avoidable  errors  have  been  discovered  which 
explain  the  chance  formation  of  nickel  and  which  undoubtedly  caused  such  a 
formation  in  the  experiments  of  Meigen  and  Bartels.  The  determination  that 
the  nickel  produced  by  a  reduction  process  in  the  oil,  is  not  capable  of  acting 
as  a  catalytic  hydrogen  conveyor,  Agde  believes  furnishes  ample  confirmation 
of  this  v'ew. 

Concerning  the  mechanics  of  the  catalytic  activity  of  nickel  oxide,  it  may  be 
noted  that  Ipatiew  has  already  advanced  the  idea,  and  Bedford  and  Erdmann 
have  brought  forth  experimental  indicat  ons  that  some  lower  oxide  of  nickel  is 
the  actual  conveyor  of  hydrogen.  But  this  does  not  exclude  the  possibility 
that  perhaps  nickel  oxide  (NiO)  is  also  capable  of  taking  up  and  transferring 
hydrogen  without  being  reduced. 

Senderens  and  Aboulenc  *  assume  the  formation  of  a  nickel  suboxide  during 

the  reduction  of  nickel  oxy hydrates  below  300°  C.     Such  an  intermediate  phase 

is  also  indicated  by  the  results  of  work  by  Sabatier  and  Espil  t  on  the  reduction 

of  nickel  oxide  in  a  current  of  hydrogen  at  different  temperatures.     For  instance, 

*Z.  angew.  Chem.,  1913,  26,  209.  fComp.  rcncl.,  1014,  158,  668. 


THE  BASE  METALS  AS  CATALYZERS  221 

when  75  per  cent  to  79  per  cent  of  the  oxygen  which  is  combined  with  the 
nickel,  is  converted  at  200°  C.  into  water,  the  curve  of  the  velocity  of  reduction 
assumes  an  entirely  different  direction,  as  the  speed  drops  greatly.  This  is  a 
sure  sign,  Agde  states,  that  an  intermediate  product,  i.e.,  a  lower  nickel  oxide, 
has  been  formed  which  is  reduced  much  more  slowly  than  the  initial  oxide. 
For  the  suboxide  formed  by  the  reduction  in  a  current  of  hydrogen,  Sabatier 
assumes  the  formula  Ni4O,  but  the  way  in  which  he  calculates  this  formula  is 
not  very  convincing  to  Agde.  In  doing  this  he  appears  to  neglect  the  fact,  that 
during  the  first  phase,  the  sharp  ascent  of  the  curve,  nickel  suboxide  is  also 
further  reduced  to  nickel,  and  also  he  does  not  take  into  consideration  the  fact 
that  the  speed  of  reaction  is  a  function  of  the  surface.  In  Agde's  opinion  the 
formula,  Ni4O,  of  Sabatier  has  no  value  other  than  to  show  that  during  the 
reduction  of  nickel  oxide  in  a  current  of  hydrogen  at  temperatures  of  180°,  200° 
C.  and  higher,  a  nickel  suboxide  is  produced  as  an  intermediate  phase. 

Agde  observes  that  the  conditions  for  the  reduction  of  the  nickel  oxide  sus- 
pended in  oil  are  materially  different  than  those  occurring  during  the  reduction 
in  a  dry  atmosphere  of  hydrogen.  If,  as  Sabatier  observed,  small  amounts  of 
water  considerably  slow  down  the  reduction  of  nickel  oxygen  compounds,  Agde 
thinks  it  is  safe  to  assume  that  large  amounts  of  fatty  oils  will  possess  such 
a  delaying  action  to  a  still  higher  degree.  At  all  events,  he  continues,  an  ex- 
planation of  the  fact  that,  as  proven,  no  nickel  is  produced  during  the  hardening 
of  the  oil,  but  that  the  reduction  here  ceases  at  an  intermediate  phase  as  a  nickel 
suboxide,  is  furnished  by  Erdmann  *  in  a  most  plausible  way  by  his  assumption 
of  an  addition  compound  of  the  nickel  oxide  with  unsaturated  fatty  substance. 
By  such  assumption  that  the  nickel  suboxide  first  formed  enters  a  complex 
compound  by  addition  and  is  shielded  from  any  further  reduction  by  hydrogen 
an  explanation  is  afforded  of  the  results  noted.  Examples  of  this  kind  are  to 
be  found  in  other  fields.  For  instance,  palladium  chloride  is  not  precipitated 
from  an  acetone  solution  by  the  introduction  of  hydrogen  as  it  combines  with 
the  ketone  to  form  a  double  compound,  while  palladium  solutions  which  do  not 
contain  such  a  double  compound  are  rapidly  reduced  to  the  metallic  state  by 
hydrogen.  That  atoms  of  a  metal  may  add  themselves  directly  to  carbon  is 
proven  by  many  examples  in  organic  chemistry,  such  as  zinc-methyl,  the  organo- 
magnesium  compounds  of  Grignard,  nickel  tetracarbonyl,  acetylene  copper  and 
acetylene-silver.  Reference  also  should  be  made  to  the  work  of  Fokin  f  on  the 
addition  of  metallic  oxides  or  of  metallic  hydroxides  to  form  double-compounds. 
This  experimenter  has  shown  that  during  the  hydrogenation  of  glycerides,  com- 
plex compounds  of  platinous  hydroxide  with  unsaturated  fats  are  produced  in 
the  form  of  sols. 

The  phenomena  which  take  place  during  the  hydrogenation  of  unsaturated 
fatty  substances  with  nickel  oxide  Agde  asserts  are  to  be  considered  in  an 
analogous  way.  The  constitution  of  this  hypothetical  addition  compound  of 
nickel  suboxide  can  be  pictured  in  the  following  way: 

I 
H— C— Niv 

I         > 
H— C— Nr 

I 

*  Oester.  Chem.  Ztg.,  16,  293,  Abstract. 

f  J.  Russian  Phys.  Chem.  Soc.,  1910,  42,  1075,  also  1912,  44,  653.  (See  Chem.  Ztg., 
1913,  37,  61,  and  Chem.  Centr.,  1910,  Part  2,  1743. 


222  THE  HYDROGENATION  OF  OILS 

In  the  further  progress  of  the  hydrogenation,  the  addition  compound,  having 
become  charged  with  hydrogen  supposedly  is  then  split  up  into  the  saturated 
fatty  substance  and  a  nickel  suboxide  containing  hydrogen,  to  which  may  be 
ascribed  the  formula: 

H— 


When  the  hydrogenation  has  progressed  so  far  that  only  a  small  amount  of 
unsaturated  compound  still  remains,  then  if  the  temperature  is  high  enough,  the 
nickel  suboxide  is  further  reduced  to  metallic  nickel  as  is  also  the  case  if  nickel 
oxide  is  treated  with  hydrogen  in  the  presence  of  stearic  acid  or  paraffin  at  250° 
C.  But  the  presence  of  the  fatty  acid  advances  the  reduction  temperature  of 
nickel  suboxide  so  high  that  the  formation  of  nickel  at  200°  C.  does  not  take 
place  even  after  treating  with  hydrogen  for  fifteen  hours. 

Certain  aromatic  substances,  such  as  acetanilide,  cinnamic  acid,  /3-naphthol, 
anthracene,  and  phenanthrene,  have,  as  Adge  was  able  to  determine,  the  prop- 
erty of  protecting  the  nickel  oxide  from  being  reduced  down  to  the  metal,  without 
taking  up  hydrogen  themselves  at  ordinary  pressure. 

Regarding  the  more  or  less  fine  division  of  the  catalyst  the  following  may  be 
noted:  An  exceedingly  fine  division  of  the  catalyst  takes  place  in  connection 
with  the  reduction  of  the  nickel  oxides  in  unsaturated  fats,  but  for  various  sub- 
stances varying  degrees  of  fineness  are  observed.  As  already  mentioned,  with 
the  glycerides,  the  degree  of  subdivision  is  actually  colloidal,  but  not  with  oleic 
acid  and  the  other  organic  compounds  used  for  the  experiments.  The  original 
supposition  of  Agde  that  the  degree  of  division  might  stand  in  relation  with  the 
viscosity  of  this  substance  has  not  been  corroborated,  for  linseed  oil  and  glycerine 
have  the  same  degree  of  viscosity  and  the  state  of  division  is  colloidal  in  the 
former,  but  not  in  the  latter,  Agde  has,  therefore,  accepted  the  assumption  of 
Bedford  and  Erdmann  that  this  division  is  related  to  the  unsaturated  condition. 
Presumably,  Agde  states,  there  is  formed  an  addition-compound  of  an  unsaturated 
organic  body  and  the  lower  nickel  oxide,  which  has  the  property  of  existing  in 
the  colloidal  condition.  The  purer  the  oils,  the  more  easily  is  a  colloidal  division 
obtained,  but  in  this  connection  the  temperature  and  the  length  of  hardening 
also  have  some  influence. 

The  hypothesis  of  the  formation  of  an  addition  compound  serves  in  the  first 
place  as  an  explanation  of  the  stability  of  the  nickel  suboxide  toward  hydrogen. 
But  other  reasons  also  bespeak  the  entrance  of  the  nickel  oxide  into  organic 
combination.  Bedford  and  Erdmann  have  already  called  attention  to  the  fact 
that  it  is  impossible  to  entirely  free  a  catalyst,  used  for  fat  hardening,  of  its 
content  of  organic  substance,  by  extracting  with  benzol,  similar  to  the  way  in 
which  Wieland  *  treated  palladium  black.  However,  Agde  found  that  the  nickel 
oxide  treated  with  hydrogen  in  molten  paraffin  or  diphenylamine  could  be 
obtained  absolutely  free  of  carbon  after  extraction  with  benzol. 

The  appearance  of  a  nickel  carbide-like  substance  Agde  believes  also  points 
with  certainty  to  a  compound  of  nickel  with  carbon.  Furthermore,  the  fact 
that  during  the  hardening  no  saponification  of  the  triolein  is  brought  about  by 

*  Ber.,  1912,  45,  488. 


,THE  BASE  METALS  AS  CATALYZERS  223 

the  nickel  oxide  leads  to  the  assumption  of  the  formation  of  an  addition-com- 
pound.* 

The  fact  that  the  hydrogenation  cannot  be  completed  with  oleic  acid,  indi- 
cates that  a  condition  of  equilibrium  takes  place  here,  between  oleic  acid,  its 
addition-compound  and  stearic  acid.  This  condition  of  equilibrium  is  constant 
at  200°  C.  but  at  250°  with  continued  introduction  of  hydrogen,  is  displaced 
and  the  nickel  suboxide  set  free  is  then  further  reduced  to  nickel. 

Another  communication  by  Normann  f  on  the  hydrogenation  of 
fats  in  the  presence  of  metallic  nickel  and  nickel  oxide  refers  to  the 
findings  of  Erdmann  that  the  hydrogenation  of  fats  is  effected  more 
rapidly  in  the  presence  of  unreduced  nickel  oxide  than  with  cata- 
lyzers of  nickel  reduced  from  such  oxide,  whereas  Normann's  experi- 
ments give  different  results,  nickel  oxide  material  being  rendered 
active  only  after  reduction  to  the  metal. 

Normann  observes  that  comparative  experiments  with  different  nickel  oxides 
and  with  the  metal  reduced  from  them  have  shown  that  the  activity  varies  with 
the  physical  form  of  the  metal.  In  the  case  of  some  forms  no  hydrogenation  could 
be  brought  about.  In  all  cases  Normann  observes  the  metal  was  superior  to 
the  oxides.  For  instance  he  notes  that  certain  impurities  in  commercial  oxides 
have  an  unfavorable  effect  upon  the  metal  reduced  therefrom.  He  found  that  a 
small  amount  of  hydrochloric  acid  had  no  effect  on  the  oxide  but  produced  a 
stimulating  effect  on  the  metal.  Salt  behaved  in  an  analogous  manner.  Sul- 
phuric acid,  he  claims,  promotes  the  activity  of  both  oxide  and  metal  catalysts 
when  present  in  small  amount.  He  also  mentions  a  fact  long  known  to  oil- 
hardening  chemists  that  the  hydrogenation  of  oils  may  be  carried  out  tech- 
nically by  means  of  metallic  nickel  without  any  carrier. 

A  series  of  comparative  tests  have  been  carried  out  by  Siegmund 
and  Suida  t  on  the  relative  value  of  nickel  and  nickel  oxide  in 
hydrogenating  oils  with  hydrogen  at  atmospheric  pressure. 

The  oils  used  were: 

A.  Linseed  oil,  iodine  number  176.2,  acid  number  6.07. 

B.  Linseed  oil,  iodine  number  170.5,  acid  number  3.58. 

C.  Cotton  oil  treated  six  hours  in  vacuo  at  150°  to  160°  C. 

with  steam  to  remove  aldehydes,  dried  for  two 
hours  in  vacuo  at  140°  to  150°  C.  in  contact  with 
hydrogen.  Iodine  number  99.2,  acid  number  0.32. 

D.  Cotton  oil,  iodine  number  105.8,  acid  number  0.89. 

E.  Rape   oil,   iodine   number   101.9,  acid   number  6.61. 

F.  Sesame  oil,  iodine  number  102.3,  acid  number  3.44. 

*  Metal  oxides  free  of  water  are  observed  always  to  have  a  saponifying  action  on  fata 
at  250.  C.  (For  literature  see  Hefter.  Technologic  der  Fette  und  Oele,  1910,  Vol.  Ill, 
623.)  Furthermore  by  the  reduction  of  NiO  to  suboxide,  some  water  is  formed. 

t  Chem.  Ztg.,  40,  757;  J.  S.  C.  I.,  35,  1070;  Chem.  Abs.,  1917,  1321. 

J  J.  Prakt.  Chemie,  1915,  442. 


224 


THE  HYDROGENATION  OF  OILS 


The  following  catalytic  materials  were  employed: 
(a)  Voluminous  nickel  oxide  prepared  according  to  Bedford  and 
Erdmann  by  dropping  small  portions  of  a  solution  of  nickel  nitrate  and 
sugar  on  a  surface  heated  to  a  low  red.  The  product  contained  carbon, 
0.42  per  cent,  hydrogen,  0.66  per  cent,  and  nickel,  76.67  per  cent.  The 
calculated  content  of  nickel  in  nickel  oxide,  NiO  is  78.57  per  cent. 

(6)  Metallic  nickel,  obtained  by  reduction  of  voluminous  nickel 
oxide  in  hydrogen  at  280°  to  290°  C. 

(c)  Basic  nickel  carbonate   (Kahlbaum). 

(d)  Nickel  formate,  prepared  by  dissolving  nickel  oxide,  or  better, 
basic  nickel  carbonate  in  warm  formic  acid,  evaporating  the  solution 
and  repeatedly   crystallizing  from  a  weak  solution  of  formic   acid. 
The   crystals   were   dried   over   sulphuric   acid.     The   product   corre- 
sponded to  the  formula  Ni(HC02)2+2H2O. 

THE  HYDROGENATING  PROCEDURE 

The  oil  was  placed  in  a  glass  flask  (Bedford  and  Erdmann  type) 
and  heated  in  an  oil  bath  to  120°  to  180°  C.  while  a  slow  stream  of 
hydrogen  was  passed  through.  The  catalyzer  was  then  added  and 
the  hydrogen  current  increased  to  15  to  20  liters  per  minute,  while 
the  temperature  was  raised  to  230°  to  260°  C.  and  was  maintained 
at  this  point  during  the  entire  hydrogenation  stage.  After  harden- 
ing, the  fat  was  filtered  from  the  catalyzer  in  an  atmosphere  of 
carbon  dioxide.  Fuller's  earth  was  added  and  a  second  filtration 
made  to  render  the  fat  free  of  catalyzer. 

NICKEL  OXIDE  AS  A  CATALYZER. 
250  g.  of  linseed  oil,  A  and  B,  were  used  in  each  of  the  following  tests. 


Test  No. 

Iodine  No. 
of  Oil  Used. 

Amt.  of 
Catalyzer 
in  Gms. 

Hardening 
Temperature. 

Liters  of 
Hydrogen 
per  Minute. 

Period  of 
Hardening, 
Hours. 

Iodine  No. 
of  Product. 

XX 

170.5 

2.5 

250-260°  C. 

18 

i 

144 

XX 

170.5 

2.5 

250-260°  C. 

18 

i 

111 

XX 

170.5 

2.5 

250-260°  C. 

18 

it 

86.6 

XX 

170.5 

2.5 

250-260°  C. 

18 

2 

62.4 

XX 

170.5 

2.5 

250-260°  C. 

18 

3 

19.8 

I 

176.2 

2.5 

240-260°  C. 

18 

31 

5.34* 

VI 

176.2 

5.0 

273-258°  C. 

10 

19 

1.05 

450  g.  cotton  oil  D  were  used  in  the  following 


VIII 

105.8 

4.5 

237° 

20 

1 

45.75 

IX 

105.8 

4.5 

239—243° 

20 

2 

16.8 

X 

105.8 

4.5 

244° 

20 

3 

5.03 

*  Solidified  at  35.2  after  two  hours;    42.5°  after  2|  hours,  and  47.4°  after  3| 
hours. 


THE  BASE  METALS  AS  CATALYZERS 


225 


HARDENING  OF  LINSEED  OIL  WITH  BASIC  NICKEL  CARBONATE. 
500  g.  Oil  A.     10  g.  Catalyzer. 


Temp. 

Time. 

Iodine  No. 

232°  C. 

1  hour 

66.9 

232-252 

2  hours 

45.3 

233-265 

3  hours 

37.3 

245-256 

4£  hours 

25.5 

HARDENING   OF  SESAME   OIL   WITH   BASIC   NICKEL   CARBONATE. 
450  g.  Oil.    6.8  g.  Catalyzer.    Temperature  241°-248°  C. 


Time. 

Iodine  No. 

Solidification  Point. 

i 

73.3 

18° 

i 

65.2 

25.6 

li 

58.0 

31.6 

2 

54.5 

34.8 

2* 

50.3 

37.7 

3 

43.8 

39.8 

COTTONSEED  OIL  C  AND  D,  RAPESEED  OIL  E  USING  BASIC  NICKEL 

CARBONATE 


Amount  of  Oil. 

Kind. 

Amount  of 
Catalyzer. 

Temp. 

Time. 

Iodine  No. 

150 

C 

3 

237-258°  C. 

2j  hours 

68.7 

280 

D 

4.2 

248°  C. 

6  hours 

26.3 

450 

E 

6.8 

248-250°  C. 

2  hours 

58.5 

LINSEED  OIL  B,   USING  A   MIXTURE   OF   METALLIC   NICKEL  AND 

NICKEL  CARBONATE 
0.15  g.  reduced  NiO  with  5.88  g.  Nickel  Carbonate. 


Temp. 

Time. 

Iodine  No. 

235-243°  C. 
240-250°  C. 

1  hour 
3  hours 

38.15 

8.4 

300  g.  oil  used  in  each  case. 

LINSEED   OIL   B,   WITH   NICKEL   FORMATE. 


Temp. 

Amount  of  Nickel  Formate. 

Time. 

Iodine  No. 

243°-257°  C. 
208°-216°  C. 

8g. 
8g. 

2  hours 
3  hours 

24.7 
3.5 

300  g.  oil  used  in  each  case. 


226 


THE  HYDROGENATION  OF  OILS 


LINSEED  OIL  A,  WITH  METALLIC  NICKEL  AS  CATALYZER. 
250  g.  Oil,  2.5  g.  Catalyzer,  Temperature  242-252°  C. 

Time.    Hours.  Iodine  No. 

\  155.7 

1  147.4 
\\  140.9 

2  134.5 
2£  126.9 

3  120.4 

If  the   values   found   for   linseed   oil   are   charted,   the   following   curves   are 
obtained,  Fig.  47d. 


From  the  curves  Siegmund  and  Suida  conclude  that  the  speed  of  reaction, 
other  things  being  equal,  is  greater  for  the  whole  reaction  period  for  nickel 
oxide  than  for  nickel  carbonate.  For  the  latter  it  is  only  very  great  at  the 
beginning  and  it  is  smallest  for  metallic  nickel.  The  mixture  of  metallic  nickel 
with  nickel  carbonate  at  first  has  the  greatest  speed  of  reaction  but  this  is  later 
surpassed  by  that  of  nickel  formate.  Meigen  and  Bartels  *  state:  "  If  water 
plays  any  role  then  the  speed  of  reaction  when  using  nickel  oxide  (as  already 
emphasized  by  Ipatiew)  must  be  initially  greater  than  with  nickel,  as  a  larger 
amount  of  water  can  be  formed  from  the  oxide.  Ipatiew  believes  that  he  has 
found  corroboration  of  this  in  his  experiments."  The  above  experiments  are 
claimed  to  be  a  new  proof  of  the  correctness  of  this  view.  The  latter  explains 
at  once  why  the  initial  speed  is  greater  when  utilizing  basic  nickel  carbonate 
or  basic  nickel  formate  as  catalysts  than  with  nickel  oxide.  That  nickel 
and  nickel  carbonate  and  particularly  nickel  formate  have  a  somewhat  greater 
reduction  catalytic  action  than  nickel  oxide  may  be  sought  for,  on  the  one 

*J,  prakt,  Chem.  (2)  89,  292,  1914. 


THE  BASE  METALS  AS  CATALYZERS  227 

hand  in  their  greater  initial  speed  of  reaction,  and  on  the  other  hand,  that  with 
them  an  oxide  poorer  in  oxygen  (nickel  suboxide)  is  more  readily  formed. 

From  the  analyses  of  the  used  and  purified  catalysts  it  appears  that  all  con- 
tain organic  substances  in  a  form  insoluble  in  benzol,  in  greater  or  lesser  amounts. 
If  we  take  into  consideration  the  fact  that  all  the  oils  used  for  the  experiments 
contain  free  fatty  acids,  the  conclusion  is  probably  justified  that  the  organic 
substance  contained  in  the  used  and  purified  catalysts  is  a  nickel  salt  of  a  fatty 
acid.  (According  to  actual  experiments  nickel  oleate  is  soluble  and  nickel 
stearate  insoluble  in  benzol).  All  used  catalysts  were  attracted  more  or  less  by 
magnets  with  the  usual  characteristic  brush  formation. 

Experiments  made  by  Siegmund  and  Suida  gave  evidence  that  on  heating 
nickel  carbonate  at  250°  C.  in  a  current  of  hydrogen  in  oils  almost  entirely 
free  of  acid,  large  amounts  of  carbon  dioxide  escape.  On  using  oils  not  free  of 
acid,  there  will  first  be  a  formation  of  nickel  soap  with  evolution  of  carbon 
dioxide. 

Nickel  formate,  was  gradually  heated  up  to  250°  C.  in  a  current  of  nitrogen 
in  a  metal  bath.  Duration  of  the  heating,  one  hour.  The  escaping  gases  were 
led  over  glowing  CuO  and  then  through  a  CaCl2  tube  and  a  potash  bulb. 

Calculated  for  Ni  (HCO2)2  +2HO*  Found 

CO2  47.37  per  cent  (  =  12.92  per  cent  C)  47.23  per  cent  (  =  12.88  per  cent  C) 
H2O  29.16  per  cent  (=  3.12  per  cent  H)  28.10  per  cent  (=  3.12  per  cent  H) 

Residue  33.83  per  cent. 

Nickel  formate  was  heated  gradually  as  above  up  to  250°  C.  for  1£  hours  in 
a  current  of  nitrogen  in  a  metal  bath.  The  escaping  gases  were  freed  of  water 
and  CO2  direct  in  the  CaCl2  tube  and  potash  bulb  without  previous  passing  over 
CuO. 

Calculated  for  Ni(HCO2)z+2H2O  Found 

CO2  47.37  per  cent  (  =  12.92  per  cent  C)  42.30  per  cent  (  =  11.54  per  cent  C) 
H2O  29.16  per  cent  (=  3.23  per  cent  H)  18.62  per  cent  (=  2.07  per  cent  H) 

Residue  34.27  per  cent. 

Accordingly  by  simple  heating  to  250°  C.  nickel  formate  is  decomposed  into 
CO2,  CO,  H2O  and  hydrogen  and  there  remains  a  product  which  in  addition  to 
31.51  per  cent  of  nickel,  in  the  main  contains  oxygen  also. 

This  residue  is  dark  grey-black  in  color  and  is  magnetic.  Its  specific  gravity 
is  5.788  at  20°  C.,  its  conductivity  is  zero.  The  composition  is  approximately 
NisO  and  the  carbonyl  test  gave  no  evidence  of  metallic  nickel.  In  order  to 
ascertain  the  behavior  of  nickel  formate  at  a  somewhat  lower  temperature,  it 
was  heated  for  1|  hours  in  a  current  of  nitrogen  to  200°  C.  In  this  time  the 
absorbing  apparatus  took  up  962  per  cent  CO.  and  11.17  per  cent  H2O,  showing 
that  nickel  formate  begins  to  decompose  at  temperatures  under  200°  C. 

The  conclusions  of  Siegmund  and  Suida  are  that:  1.  Under  ordinary  pressure 
the  hardening  of  fat  takes  place  incomparably  more  rapidly  with  nickel  oxide 
than  with  metallic  nickel.  2.  When  using  nickel  carbonate  and  nickel  formate 
as  catalysts  the  hardening  of  fat  proceeds  exactly  in  the  same  way  as  when  nickel 
oxide  is  used.  3.  The  used  catalysts  obtained  when  nickel  oxide,  nickel  carbon- 
ate, nickel  formate  and  metallic  nickel  -{-nickel  carbonate  are  used  have  approxi- 


228  THE  HYDROGENATION  OF  OILS 

mately  the  same  composition.  4.  The  hardening  of  fat  with  nickel  carbonate, 
nickel  formate,  or  a  mixture  of  nickel + nick  el  carbonate  is  identical  with  the 
hardening  when  using  nickel  oxide.  In  this  hardening  a  low  oxide  of  n  ckel  is 
the  conveyor  of  the  hydrogen.  This  hardening  is  materially  different  from  that 
made  with  metallic  nickel.  5.  In  those  hydrogenation  processes  in  which  a  low 
nickel  oxide  is  the  hydrogen  conveyor,  water  plays  a  role. 


CHAPTER    IX 
NICKEL  CARBONYL 

Owing  to  the  interest  manifested  in  nickel  carbonyl  as  a  source  of 
catalytic  nickel  and  because  of  the  difficulties  encountered  in  its  prepa- 
ration the  following  extracts  from  various  publications  on  the  subject 
are  appended. 

The  action  of  carbon  monoxide  on  nickel  was  noted  by  Mond  and 
associates  in  1890.*  When  carbon  monoxide  is  passed  over  finely- 
divided  nickel,  such  as  is  obtained  by  reducing  nickel  oxide  by  hydro- 
gen at  about  400  degrees,  at  a  temperature  between  350  and  450  de- 
grees, carbon  dioxide  is  formed,  and  the  nickel  is  gradually  converted 
into  a  black,  amorphous  powder,  consisting  of  carbon  and  nickel; 
the  composition  of  this  deposit  varies  widely  with  temperature  and 
time.  A  small  quantity  of  nickel  can  thus  change  a  very  large  amount 
of  carbon  monoxide,  the  action  being  complete  and  rapid  at  first,  and 
continuing,  although  at  a  diminishing  rate,  for  several  weeks.  A 
product  containing  as  much  as  85  parts  carbon  to  15  parts  nickel  was 
obtained.  Acids  only  partially  remove  the  nickel;  the  carbon  is  very 
readily  acted  on  by  steam,  carbon  dioxide  and  hydrogen  without  a 
trace  of  carbon  monoxide  being  formed  at  a  temperature  of  350  degrees. 

On  allowing  the  substance  to  cool  in  a  current  of  carbon  monoxide, 
it  was  noticed  that  the  flame  of  a  Bunsen  burner  into  which  the  escap- 
ing gas  was  introduced  became  luminous,  and  when  the  tube  through 
which  the  gas  passed  was  heated,  a  deposit  of  nickel,  mixed  with  a 
small  quantity  of  carbon,  was  obtained.  Mond  and  his  associates 
were  thus  led  to  discover  the  existence  of  a  volatile  nickel  compound. 

To  prepare  this  compound  a  combustion  tube  was  filled  with  nickel 
oxide  and  this  was  reduced  by  hydrogen  at  about  400  degrees;  after 
cooling  the  nickel  to  about  100  degrees,  pure  dry  carbon  monoxide 
was  passed  over  it  without  further  heating,  and  the  issuing  gas  led 
through  a  tube  placed  in  a  freezing  mixture;  the  major  portion  of  the 
nickel  compound  condensed  as  a  colorless  liquid;  but  since  the  gas 
retained  about  5  per  cent,  it  was  collected,  dried  and  again  passed  over 
the  metal.  When  no  more  liquid  condensed,  the  nickel  was  again 

*  Mond,  Langer  and  Quincke,  Proc.  Chem.  Soc.  (1890),  112;  J.  S.  C.  I.  (1890), 
808. 

229 


230  THE  HYDROGENATION  OF  OILS 

heated  to  about  400  degrees  in  a  slow  current  of  pure  carbon  monoxide ; 
it  was  then  cooled  to  about  100  degrees,  and  again  submitted  to  the 
action  of  the  gas. 

Nickel  carbonyl  thus  prepared  is  a  colorless  liquid,  which  boils  at 
43  degrees  under  751  mm.  pressure;  its  relative  density  at  17  degrees 
is  1.3185.  It  solidifies  at  -25  degrees  to  a  mass  of  needle-shaped 
crystals.  Its  composition  is  represented  by  the  formula  Ni(CO)4. 
It  dissolves  in  alcohol,  and  more  readily  in  benzene  and  chloroform; 
dilute  acids  and  alkalis  have  no  action  on  it,  but  it  is  oxidized  by  con- 
centrated nitric  acid.  It  reduces  an  ammoniacal  solution  of  cupric 
chloride,  and  also  causes  the  separation  of  silver  from  an  ammoniacal 
solution  of  silver  chloride.  It  interacts  with  chlorine,  forming  nickel 
chloride  and  carbon  oxychloride.  It  is  decomposed  at  180  degrees 
(in  boiling  aniline  vapor)  into  nickel  and  carbon  monoxide.  The 
atomic  weight  of  the  deposited  metal  was  found  in  three  experiments 
to  be  58.52  to  58.64,  a  result  closely  corresponding  with  Russell's 
value,  58.74. 

Numerous  experiments  to  obtain  similar  compounds  with  other  metals,  notably 
with  cobalt,  iron,  copper  and  platinum,  led  to  negative  results.  On  experimenting 
with  specially-purified  cobalt,  in  the  beginning  a  slight  coloration  of  the  Bunsen 
flame  into  which  the  gas  was  led  was  noticed,  but  after  a  time  this  was  no  longer 
observed.  Commercial  cobalt  afforded  a  gas  which  deposited  a  mirror  of  pure 
nickel,  it  being  possible,  in  fact,  to  purify  cobalt  from  nickel  by  carbonic  oxide. 
The  nickel  mirrors  obtained  by  heating  the  carbonic  oxide  compound  do  not  appear 
to  contain  any  trace  of  cobalt. 

Martha  (Chem.  Ztg.  (1891),  915;  J.  S.  C.  I.,  1891,  837)  has  recorded  some  prop- 
erties of  nickel  carbonyl  which  are  of  interest.  He  used  some  impure  ferriferous 
nickel  oxide  as  the  source  of  the  metal.  Under  these  circumstances  the  condensed 
nickel  compound  has  always  a  yellow  tinge,  and  contains  iron,  as  do  also  the  nickel 
films  obtained  by  heating  the  conducting  tube.  The  liquid  after  standing  for  a 
few  hours,  even  in  a  sealed  tube,  deposits  a  brown  compound  containing  iron,  which 
often  explodes  with  great  violence  when  the  liquid  is  poured  off,  the  sides  of  the  tube 
being  simultaneously  covered  with  a  film  of  nickel.  An  apple  green  precipitate 
containing  nickel  is  occasionally  deposited,  together  with  the  brown  iron  compound, 
and  adheres  strongly  to  the  sides  of  the  tube.  The  vapor  of  the  liquid  compound 
exploded  upon  one  occasion  very  violently,  either  owing  to  the  presence  of  a  particle 
of  the  iron  compound  or  to  its  own  explosive  properties. 

Berthelot  *  notes  that  the  vapor  tension  of  nickel  carbonyl  (boiling 
point  46°  C.)  at  16°  C.  is  about  one-fourth  of  an  atmosphere.  A  drop 
of  the  liquid  allowed  to  evaporate  spontaneously  forms  a  certain 
quantity  of  crystals,  which  consist  of  the  solidified  substance,  and 
speedily  volatilize  on  continued  exposure.  It  has  no  sensible  tension 
of  dissociation  at  the  ordinary  temperature,  but  in  contact  with  air 

*  Bull.  Soc.  Chim.  (1892),  13,  431. 


NICKEL   CARBONYL  231 

oxidizes  rapidly.  The  precise  mechanism  of  oxidation  varies  accord- 
ing to  the  conditions  under  which  it  takes  place.  For  example,  when 
an  inert  gas,  charged  with  the  vapor  of  nickel  carbonyl,  is  passed 
through  a  strongly  heated  tube,  the  products  are  metallic  nickel  and 
carbon  monoxide,  as  observed  by  Mond  and  his  colleagues.  These 
investigators  also  found  when  nickel  carbonyl  is  heated  sharply  to 
70°  C.,  at  which  point  detonation  takes  place,  that  the  same  bodies 
are  formed. 

Berthelot,  however,  has  observed  that  a  certain  amount  of  carbon  dioxide  and 
carbon  is  produced.  He  is  of  the  opinion  that  this  reaction  determines  the  occur- 
rence of  the  detonation,  as  the  equation 

2  CO  =  CO2  +  C 

implies  the  evolution  of  38.8  calories,  i.e.,  77.6  calories  for  the  4  mols.  of  carbon 
monoxide  in  Ni(CO)4.  The  only  assumption  necessary  to  justify  this  view  is  that 
the  heat  of  combination  of  Ni  and  CO  is  less  than  77.6  calories. 

The  reactions  of  nickel  carbonyl  are  generally  those  dependent  upon 
the  presence  in  it  of  nickel,  but  when  they  are  induced  gently  and  at 
low  temperature,  bodies  comparable  to  organo-metallic  compounds 
are  formed.  The  vapor  of  nickel  carbonyl  is  not  sensibly  soluble  in 
water  or  dilute  acid  or  alkaline  solutions  or  cuprous  chloride.  Hydro- 
carbons are  its  natural  solvents;  spirits  of  turpentine  is  specially 
suitable,  and  can  be  used  for  determining  it.  Explosion  of  a  mixture 
of  nickel  carbonyl  and  oxygen  can  be  effected  by  violent  agitation  over 
mercury  as  well  as  by  direct  ignition.  Slow  union  takes  place  when 
such  a  mixture  is  kept  in  contact  with  a  little  water.  In  contact  with 
strong  sulfuric  acid  dry  liquid  nickel  carbonyl  explodes  after  a  short 
interval,  but  if  in  the  form  of  vapor  and  diluted  with  nitrogen  it  is 
decomposed  gradually,  the  theoretical  quantity  of  carbon  monoxide 
being  liberated.  Strong  caustic  potash  has  no  perceptible  action  on 
nickel  carbonyl.  Gaseous  ammonia  does  not  act  immediately  per  se, 
but  if  a  little  oxygen  be  added,  fumes  are  produced,  and  if  the  action 
of  oxygen  be  continued  a  whitish  deposit  of  complex  composition  is 
gradually  formed  which  is  destroyed  with  charring  on  being  heated. 

Sulfuretted  hydrogen  acts  on  nickel  carbonyl  vapor,  mixed  with 
nitrogen  in  the  cold,  a  black  sulfide  (of  nickel)  being  precipitated. 
Phosphoretted  hydrogen  under  similar  conditions  gives  a  brilliant 
black  deposit.  Nitric  oxide  if  mixed  with  nickel  carbonyl  vapor, 
diluted  with  nitrogen,  or  passed  into  the  liquid  itself,  produces  blue 
fumes,  which  fill  the  whole  vessel.  The  formation  of  nickel  carbonyl 
proves  carbon  monoxide  to  be  capable  of  forming  organo-metallic 
compounds  similar  to  those  derived  from  hydrocarbons,  and  analogous 
to  the  salts  of  rhodizonic  and  croconic  acids  produced  by  the  union  of 


232  THE  HYDROGENATION  OF  OILS 

the  condensed  derivatives  of  carbon  monoxide  with  an  alkaline  metal. 
Nickel  carbonyl  serves  as  an  example  of  the  tendency  of  carbon  mon- 
oxide to  form  loose  combinations  and  products  of  condensation,  in 
virtue  of  its  character  as  an  unsaturated  body. 

Nickel  carbonyl,  according  to  Berthelot,*  can  be  preserved  under 
water,  but  if  contained  in  a  bottle  with  an  ordinary  ground-in  stopper 
becomes  slowly  oxidized,  and  a  layer  of  apple  green  nickel  hydrate  is 
formed,  which  is  free  from  carbon.  A  portion  of  it,  however,  makes  its 
way  out  of  the  bottle  and  is  oxidized,  forming  a  fume  which  is  deposited 
on  adjacent  objects. 

In  order  to  examine  the  product  of  oxidation  Berthelot  kept  a  bottle  of  nickel 
carbonyl  in  a  double  casing  of  tin  plate  and  succeeded  in  collecting  a  few  decigrams 
of  a  complex  oxide,  which  appeared  white  in  small  quantity,  but  had  a  greenish 
tinge  when  viewed  in  mass.  It  was  found  to  be  the  hydrated  oxide  of  an  organo- 
metallic  compound  of  nickel,  and  upon  analysis  gave  figures  corresponding  to  the 
formula  C2OjNia  •  10  H^O.  It  therefore  appears  to  be  the  oxide  of  a  complex  radical 
analogous  to  croconic  and  rhodizonic  acids. 

The  fact  that  under  ordinary  circumstances  nickel  alone  is  acted  on  when  a 
mixture  of  this  metal  with  any  other  metallic  or  mineral  substance  is  treated  by 
carbonic  oxide  gas,  led  Mond  (J.  S.  C.  I.,  1891,  836)  to  institute  experiments  to 
ascertain  whether  it  would  not  be  possible  by  means  of  carbonic  oxide  to  extract 
nickel  direct  from  its  ores,  and  such  metallurgical  products  as  nickel  speiss  and  nickel 
matte.  As  the  nickel  is  volatilized  at  the  ordinary  temperature  in  the  form  of  a 
vapor  disseminated  through  other  gases  from  which  it  can  be  deposited  without 
first  condensing  the  nickel  compound,  by  simply  heating  these  gases  to  the  moderate 
temperature  of  200°  C.,  as  it  is  thus  obtained  in  the  form  of  bright  coherent  masses 
of  great  purity,  as  the  carbonic  oxide  used  is  completely  liberated  and  can  be  em- 
ployed over  and  over  again,  and  as  small  quantities  of  the  poisonous  nickel  com- 
pound which  may  escape  decomposition  would  thus  never  leave  the  closed  apparatus 
in  which  the  process  would  be  carried  out,  it  seemed  probable  that  such  a  process 
might  be  capable  of  industrial  application,  and  might  prove  more  economical  than 
the  complicated  operations  metallurgists  have  to  resort  to  to  produce  tolerably  pure 
nickel. 

Experiments  carried  out  in  conjunction  with  Langer,  with  a  great  variety  of 
nickel  ores  from  all  parts  of  the  world,  containing  from  4  to  40  per  cent  of  nickel, 
as  well  as  a  number  of  samples  of  nickel  speiss  and  nickel  matte,  proved  that  as 
long  as  the  nickel  is  combined  with  arsenic  or  sulfur  the  process  was  successful. 
In  the  majority  of  cases  Mond  was  able  to  extract  the  nickel  almost  completely  in 
three  or  four  days.  Such  ores  or  matte  or  speiss  have  in  the  first  instance  to  be 
calcined,  so  as  to  convert  the  nickel  completely  into  oxide.  The  mass  is  then  reduced 
in  a  current  of  hydrogen-containing  gases — in  practice  water  gas  at  a  temperature 
of  450°  C.  It  is  cooled  down  to  ordinary  temperature  and  treated  with  any  good 
apparatus  for  treating  solids  by  gases.  Methodical  apparatus  moving  the  reduced 
ore  in  opposite  directions  to  the  current  of  carbon  monoxide,  at  the  same  time  exposing 
fresh  surfaces,  facilitate  the  operation.  After  a  certain  time  the  action  of  the  car- 
bon monoxide  upon  the  nickel  becomes  sluggish.  The  mass  is  then  heated  to  about 

_*  Bull  Soc,  Chim.  (1892),  434, 


NICKEL   CARBONYL  233 

350°  C.  in  a  current  of  carbon  monoxide,  which  regenerates  the  activity  of  the  nickel. 
This  may  be  done  in  the  same  apparatus,  but  it  is  preferable  to  use  a  separate  appa- 
ratus connected  with  the  first,  and  from  which  the  material  is  returned  to  the  first 
by  mechanical  means,  so  that  each  apparatus  can  be  kept  at  the  same  temperature. 
The  carbon  monoxide  gas  can  be  employed  dilute,  as  it  is  obtained  from  gas  pro- 
ducers; but  since  it  is  continuously  recovered,  a  purer  gas,  such  as  can  be  cheaply 
prepared  by  passing  carbon  dioxide  through  incandescent  coke,  is  more  advanta- 
geous, as  it  extracts  the  nickel  more  quickly  and  requires  smaller  apparatus.  The 
gas  charged  with  the  nickel  compound  leaving  the  apparatus  is  passed  through  tubes 
or  chambers  heated  to  about  200°  C.,  in  which  the  nickel  is  deposited.  The  gas 
leaving  these  tubes  is  returned  to  the  first  apparatus,  and  circulates  continuously. 
From  time  to  time  the  nickel  is  removed  from  the  tubes  in  which  it  has  been 
deposited.  To  facilitate  this  operation  thin  nickel  sheets,  bent  to  fit  the  tubes, 
are  inserted,  on  which  the  nickel  deposits,  and  which  are  easily  taken  out.  The 
metal  so  obtained  is  almost  chemically  pure;  only  very  rarely  in  the  case  of  certain 
ores  it  is  slightly  contaminated  with  iron.  As  the  nickel  is  deposited  in  perfectly 
coherent  films  upon  heated  surfaces  exposed  to  the  gas  containing  the  nickel  car- 
bonyl,  it  was  found  possible  to  produce  direct  from  such  gas,  articles  of  solid  nickel 
or  goods  plated  with  nickel.  This  result  can  also  be  obtained  by  immersing  heated 
articles  in  a  solution  of  nickel  carbonyl  in  such  solvents  as  benzole,  petroleum,  tar  oils, 
etc.,  or  by  applying  such  solution  to  the  heated  articles  with  a  brush  or  otherwise. 

Mond  *  observes  that  a  mixture  of  the  vapor  and  air  explodes  readily 
but  not  very  violently.  The  pure  liquid  does  not  explode,  but  at  high 
temperatures  it  decomposes.  The  vapor  has  a  characteristic  odor 
and  is  poisonous.  It  produces  an  extraordinary  reduction  of  tempera- 
ture when  injected  subcutaneously,  sometimes  as  much  as  12  degrees. 
The  liquid  can  be  distilled,  but  not  from  solution  in  liquids  of  a  higher 
boiling  point  as  decomposition  then  occurs,  finely-divided  nickel  being 
separated  and  carbonic  oxide  being  evolved. 

When  attacked  by  oxidizing  agents,  e.g.,  nitric  acid,  chlorine,  or  bromine  or  by 
sulfur,  decomposition  ensues,  nickel  salts  being  formed  and  carbon  dioxide  liber- 
ated. Metals,  alkalies,  non-oxidizing  acids  and  the  salts  of  other  metals  produce  no 
change.  Nickel  carbonates  of  composition  varying  with  the  hygroscopic  state  of 
the  atmosphere  are  formed  by  exposing  the  liquid  to  the  action  of  the  air.  These 
precipitates  dissolve  easily  in  dilute  acid.  An  intense  blue  coloration  is  obtained 
when  nitric  oxide  is  passed  through  a  solution  of  nickel  carbonyl  in  alcohol  (Berthelot). 

Nickel  carbonyl  is  very  diamagnetic,  and  an  almost  perfect  non-conductor  of 
electricity  (Quincke).  All  other  nickel  compounds  are  paramagnetic.  It  is  opaque 
for  rays  beyond  the  wave  length  3820,  and  its  flame  gives  a  continuous  spectrum 
(Liveing  and  Dewar). 

Perkin  found  the  power  of  magnetic  rotation  of  nickel  carbonyl  to  be  greater 
than  that  of  any  other  substance  he  has  examined,  except  phosphorus.  Mond  and 
Nasini  found  the  atomic  refraction  to  be  about  2.5  times  as  large  as  in  any  other 
nickel  compound,  and  the  former  proved  it  to  have  great  refractive  and  dispersive 
powers.  The  atomic  refraction  of  a  liquid  ferro-carbonyl  bears  about  the  same 

*  J.  S.  C.  I.,  1892,  750. 


234 


THE  HYDROGENATION  OF  OILS 


ratio  to  the  atomic  refraction  of  other  iron  compounds.  This  ferro-carbonyl  is 
similar  in  preparation  and  properties  to  the  nickel  carbonyl,  and  at  180°  C.  the  iron 
is  thrown  down  in  bright  mirror-like  form,  carbon  monoxide  being  liberated.  Its 
composition  is  Fe(CO)s. 

To  extract  nickel  from  its  ores  Mond  used  an  apparatus,  Fig.  48, 
consisting  of  a  cylinder  divided  into  many  compartments,  through 
which  the  properly  prepared  ore  is  passed  very  slowly  by  means  of 
stirrers  attached  to  a  shaft.  On  leaving  the  bottom  of  this  cylinder 
the  ore  passes  through  a  transporting  screw,  and  from  this  to  an 
elevator  which  returns  it  to  the  top  of  the  cylinder,  so  that  it  passes 
many  times  through  the  cylinder  until  all  the  nickel  is  volatilized. 
Into  the  bottom  of  this  cylinder  carbonic  oxide  is  passed,  which  being 
charged  with  nickel  carbonyl  vapor  leaves  at  the  top,  and  passes 
through  the  conduits  shown  into  tubes  set  in  a  furnace,  and  heated 
to  200°  C.  Here  the  nickel  separates  from  the  nickel  carbonyl.  The 
carbonic  oxide  is  regenerated  and  taken  back  to  the  cylinder  by  means 
of  a  fan,  so  that  the  same  gas  is  made  to  carry  fresh  quantities  of  nickel 
out  of  the  ore  in  the  cylinder,  and  to  deposit  it  in  the  tubes  an  infinite 
number  of  times.  When  the  carbonic  oxide  comes  out  at  the  top  of 


FIG.  48. 


the  cylinder  it  passes  through  a  filter  to  catch  any  dust  it  may  contain. 
The  carbonic  oxide,  on  escaping  from  the  depositing  tubes,  is  passed 
through  another  filter,  thence  through  a  lime  purifier  to  absorb  any 
carbon  dioxide  which  may  have  been  formed.  By  means  of  this 
apparatus  nickel  has  been  extracted  from  a  great  number  of  ores,  in 
times  varying,  according  to  the  nature  of  the  ores,  from  a  few  hours  to 
several  days. 

A  review  by  Mond  of  his  experimental  work  on  nickel  carbonyl  * 
is  instructive. 

*    J,  S.  C.  I.,  1895,  945. 


NICKEL   CARBONYL  235 

Mond  stated  that  "in  the  course  of  these  experiments  finely-divided  nickel, 
formed  by  reducing  nickel  oxide  at  400°  C.  by  hydrogen,  was  treated  with  pure  CO 
in  a  glass  tube,  at  varying  temperatures,  for  a  number  of  days,  and  was  then  cooled 
down  in  a  current  of  CO  before  it  was  removed  from  the  tube.  In  order  to  keep 
the  poisonous  CO  out  of  the  atmosphere  of  the  laboratory,  we  simply  lit  the  gas 
escaping  from  the  apparatus.  To  our  surprise  we  found  that,  while  the  apparatus 
was  cooling  down,  the  flame  of  the  escaping  gas  became  luminous  and  increased  in 
luminosity  as  the  temperature  got  below  100°  C.  On  a  cold  plate  of  porcelain  put 
into  this  luminous  flame,  metallic  spots  were  deposited  similar  to  the  spots  of  arsenic 
obtained  with  a  Marsh  apparatus;  and  on  heating  the  tube  through  which  the  gas 
was  escaping  we  obtained  a  metallic  mirror,  while  the  luminosity  disappeared." 

"At  the  first  moment  we  thought  that  there  must  be  an  unknown  element  in  our 
nickel  giving  rise  to  the  production  of  this  effect,  but  when  we  examined  the  mirrors 
we  found  them  to  consist  of  pure  nickel.  As  it  seemed  so  very  improbable  that  so 
heavy  a  metal  as  nickel  should  form  a  readily  volatile  compound  with  CO,  we  puri- 
fied our  CO  as  perfectly  as  possible  but  still  obtained  the  same  results." 

"We  now  endeavored  to  isolate  this  curious  and  interesting  substance  by  prepar- 
ing the  nickel  with  great  care  at  the  lowest  possible  temperature,  and  treating  this 
nickel  with  CO  at  about  50°  C.,  and  thus  we  gradually  increased  the  amount  of  the 
volatile  nickel  compound  in  the  gases  passing  through  the  apparatus.  We  absorbed 
the  excess  of  CO  by  cuprous  chloride  solution,  and  thus  obtained  a  residue  of  several 
cubic  centimeters,  containing  the  volatile  nickel  compound  mixed  with  a  little 
nitrogen.  By  passing  this  gas  through  a  heated  tube  we  separated  the  nickel,  obtain- 
ing an  increased  volume  of  gas,  and  found  in  this  a  quantity  of  CO  corresponding  to 
about  four  equivalents  for  one  equivalent  of  nickel.  By  further  improving  our 
method  of  preparing  the  finely-divided  nickel  and  by  passing  the  resulting  gas 
through  a  refrigerator,  cooled  by  snow  and  salt,  we  at  last  succeeded  in  liquefying 
this  compound,  and  were  able  to  produce  it  with  ease  and  facility  in  any  quantity 
we  desired."  Nickel  carbonyl  "is  soluble  in  alcohol,  petroleum  and  chloroform; 
it  is  not  acted  upon  by  dilute  acids  or  alkalies,  and  can  be  readily  distilled  without 
decomposition.  But  on  heating  the  gas  to  150°  C.,  it  is  completely  dissociated  into 
its  components,  pure  CO  being  obtained  and  the  nickel  being  deposited  in  a  dense 
metallic  film  upon  the  sides  of  the  vessel  in  which  it  is  heated. " 

"  For  a  long  time,  while  we  were  engaged  in  investigating  the  physical  and  chem- 
ical properties  of  this  interesting  substance  —  which  was  without  parallel  in  the 
history  of  chemistry  —  and  while  we  were  endeavoring  to  obtain  other  similar  com- 
pounds with  other  metals,  I  had  myself  no  suspicion  that  this  substance,  which  was 
until  then  only  obtainable  by  very  careful  and  elaborate  laboratory  manipulations, 
should  ever  become  available  for  industrial  purposes.  But  the  longer  we  went  on 
preparing  it  for  our  investigations,  the  more  easy  we  found  it  to  prepare  it  in  quan- 
tity, after  we  once  knew  exactly  the  best  conditions  for  so  doing.  After  that  I 
came  to  the  conclusion  that  it  ought  to  be  possible  to  make  use  of  the  ease  with 
which  nickel  is  converted  into  a  volatile  gas  by  CO,  while  practically  all  other  metals, 
and  notably  cobalt  (which  is  so  difficult  to  separate  from  nickel  by  other  methods), 
was  not  acted  upon  by  this  gas,  for  separating  nickel  from  cobalt  and  other  metala 
on  a  manufacturing  scale,  and  for  obtaining  it  in  a  very  pure  state." 

"I  erected  a  plant  on  a  large  scale  near  Birmingham,  and  after  several  years  of 
hard  work,  during  which  the  apparatus  has  had  to  be  several  times  reconstructed 
so  as  to  fulfil  all  the  conditions  of  this  rather  delicate  process,  we  have  succeeded 
in  our  object,  and  now  have  for  some  time  produced  nickel  at  the  rate  of  a  ton  and 


236  THE  HYDROGENATION  OF  OILS 

a  half  per  week  from  the  Canadian  nickel  copper  matte  imported  into  England. 
This  matte,  which  contains  about  40  per  cent  of  nickel,  and  an  equal  quantity  of 
copper,  is  carefully  roasted  to  drive  out  the  sulfur  as  far  as  possible,  and  is  then 
subjected  to  the  action  of  hydrogenous  gases,  either  water  gas  or  producer  gas,  rich 
in  hydrogen,  in  an  apparatus  which  is  called  the  'reducer,'  the  temperature  of 
which  is  under  perfect  control,  so  that  400°  C.  is  never  exceeded.  From  this  appar- 
atus the  substance,  which  is  now  reduced  to  the  metallic  state,  is  taken  through  air- 
tight conveyors  and  elevators  into  another  apparatus  called  the  '  volatilizer, '  in 
which  it  is  subjected,  at  a  temperature  not  exceeding  80°  C.,  to  the  action  of  CO 
gas." 

"This  apparatus  consists  of  an  iron  cylinder,  divided  into  numerous  compart- 
ments by  shelves,  and  provided  with  a  stirring  device,  which  gradually  moves  the 
material  from  the  top  to  the  bottom,  while  the  CO  gas  passes  through  in  an  opposite 
direction.  The  CO  gas,  which  should  be  as  rich  as  practicable,  we  prepare  by  pass- 
ing pure  CO2  through  incandescent  coke;  the  pure  CO2  we  make  by  passing  the  flue 
gas  of  a  boiler  or  of  a  fire  through  a  solution  of  carbonate  of  potash,  and  subsequently 
boiling  the  solution.  The  CO  gas,  charged  with  nickel  carbonyl,  leaving  the  volatil- 
izer, is  passed  through  a  series  of  tubes  or  chambers,  heated  to  about  180°  C.,  in 
which  the  nickel  is  deposited  in  various  forms,  according  to  the  speed  of  the  gas 
current,  the  richness  of  the  gas  and  the  existing  temperature.  The  CO  gas,  thus 
almost  completely  freed  from  the  nickel,  is  taken  back  by  means  of  a  blower  into 
the  volatilizer,  where  it  takes  up  a  fresh  quantity  of  nickel  and  is  constantly  used 
over  and  over,  so  that  the  quantity  consumed  is  limited  to  the  very  small  amount 
of  unavoidable  loss  through  leakage  of  the  plant." 

"The  material  under  treatment  is  repeatedly  taken  from  the  volatilizer  to  the 
reducer  and  vice  versa,  by  means  of  air-tight  conveyors  and  elevators,  until  the 
amount  of  nickel  volatilized  begins  to  fall  off.  It  is  then  roasted  again  to  remove 
the  sulfur  which  it  still  contains,  and  is  treated  by  sulfuric  acid  to  dissolve  part  of 
the  copper.  The  residue,  containing  nickel,  some  copper  and  the  other  impurities 
of  the  matter  is  again  subjected  to  the  previously  described  treatment  until  the 
nickel  has  been  extracted  as  far  as  practicable;  and  the  ultimate  residue,  still  con- 
taining a  few  per  cent  of  nickel,  is  melted  up  into  matte  again." 

Nickel  carbonyl  is  decomposed  *  by  passage  through  a  mass  of  pel- 
lets of  metallic  nickel,  heated  to  about  200°  C.,  causing  nickel  to  be 
deposited  and  the  pellets  to  increase  in  size.  The  apparatus  con- 
sists of  a  vertical  cylinder,  in  which  the  pellets  are  placed,  with  heat- 
ing spaces  formed  by  an  outer  casing.  A  vertical,  cooled,  perforated 
tube  for  the  gaseous  carbonyl  leads  from  the  top  down  the  center  of 
the  mass  of  pellets,  nearly  to  the  bottom  of  the  cylinder.  To  prevent 
the  pellets  cohering,  they  are  kept  in  motion  by  continuously  with- 
drawing them  from  the  lower  end,  mechanically  screening  them  with 
the  assistance  of  worm  conveyors,  and  returning  the  small  ones  by  an 
elevator  to  a  feeding  hole  at  the  upper  end  for  further  treatment  with 
the  carbonyl.  The  pellets  which  have  sufficiently  increased  in  size 
are  passed  from  the  screen  and  thence  through  a  valved  opening  into 
a  collecting  chamber. 

*  Mond,  British  Patent  1106,  Jan.  14,  1898. 


.NICKEL   CARBON YL  237 

In  extracting  nickel  by  means  of  carbon  monoxide  from  mixtures 
of  nickel  and  other  metals,  obtained  by  reducing  the  mixed  oxide  with 
gas  containing  carbon  monoxide,  Fierz  *  displaces  the  carbon  monoxide 
by  hydrogen  or  removes  it  by  suction  from  the  presence  of  the  re- 
duced metals  while  the  temperature  is  maintained  above  that  at  which 
nickel  will  decompose,  or  combine  with,  carbon  monoxide.  The 
temperature  is  then  reduced  to  that  required  for  the  formation  of 
nickel  carbonyl  and  the  gas  readmitted. 

Longer  f  describes  an  apparatus  for  obtaining  nickel  from  nickel 
carbonyl.  Vessels  containing  the  nickel  carbonyl  are  heated  by  a 
number  of  gas  flames,  each  of  which  is  situated  in  a  chamber  formed 
by  ribs  on  the  vessel  and  an  outer  casing;  the  liberated  gases  pass  away 
by  an  escape  pipe,  which  is  surrounded  by  an  annular  cooling  chamber,  f 

James  Dewar  §  remarks  that  the  nickel  carbonyl  vapor  at  ordinary 
pressures  is  very  unstable,  its  components  becoming  rapidly  disso- 
ciated with  explosion  on  moderate  elevation  of  temperature,  so  that 
its  production  has  hitherto  been  carried  on  at  a  moderately  low  tem- 
perature, such  as  50°  C.  Dewar  has  found  that  under  considerable 
pressure,  ranging  from  2  atmospheres  to  100  atmospheres,  the  com- 
pound, either  as  vapor  or  as  liquid,  is  much  more  stable,  and  there- 
fore higher  temperatures  can  be  used  in  its  production,  whereby  the 
rapidity  of  process  of  manufacture  is  greatly  increased.  Thus  for  the 
gasification  of  the  nickel  a  temperature  of  100°  C.  with  a  pressure  of 
15  atmospheres  is  suitable,  or  a  temperature  of  180°  C.  with  a  pres- 
sure of  80  atmospheres.  The  spongy  nickel  obtained  by  the  reduction 
by  means  of  water  gas,  if  treated  at  the  temperature  and  pressure 
mentioned,  combines  rapidly  with  the  carbonic  oxide,  producing  vapor 
of  nickel  carbonyl.  This  vapor,  with  the  excess  of  carbonic  oxide  in 
which  it  is  diffused  while  still  under  pressure,  on  being  passed  through 
tubes  of  a  higher  temperature,  becomes  dissociated  depositing  metallic 
nickel.  || 

In  the  author's  laboratory  nickel  carbonyl  has  been  extensively 
examined  and  has  proved  a  satisfactory  source  of  nickel  catalyzer. 
The  carbonyl  readily  decomposes  at  temperatures  between  125°  and 
180°  C.  and  when  decomposed  in  the  presence  of  oil  under  some  con- 
ditions the  resulting  nickel  is  very  finely  divided  and  imparts  to  the 

*  British  Patent  4249,  Feb.  19,  1913. 
t  British  Patent  13,350,  June  28,  1905. 

J  See  also  U.  S.  Patent  815,717,  Mar.  20,  1906;  825,844,  July  10,  1906;  and 
865,969,  Sept.  10,  1907. 

§  U.  S.  Patent  760,852,  May  24,  1904. 

U  Electrochem.  and  Met.  Ind.  (1904),  291. 


238  THE  HYDROGENATION  OF  OILS 

oil  an  inky  black  color.  Even  after  standing  for  days  or  even  weeks 
the  nickel  remains  in  suspension.  A  sample  of  cottonseed  oil  carrying 
about  one-half  of  one  per  cent  of  nickel  precipitated  from  nickel  car- 
bonyl  was  exposed  to  the  action  of  a  current  of  hydrogen  gas  under 
practically  atmospheric  pressure  for  a  period  of  one  hour  and  a  solid 
product  resulted  having  a  melting  point  of  47.6°  C.  and  a  refractive 
index  of  1.4445. 


FIG.  49.  —  Photo-micrograph  of  Nickel  Catalyzer  derived  from 
Nickel  Carbonyl.     X  100. 

The  greatest  difficulty  in  the  use  of  nickel  carbonyl  appears  to  be 
the  removal  of  finer  portions  of  the  nickel  precipitate  from  the  oil 
after  hydrogenation,  but  this  may  be  accomplished  by  the  observance 
of  due  precaution  in  filtration.  The  used  catalyzer  recovered  by  filtra- 
tion is  still  active  and  may  be  used  until  its  catalytic  properties  are 
spent.  The  spent  material  may  be  regenerated  more  easily  than  is 
the  case  with  catalyzers  consisting  of  nickel  supported  on  a  voluminous 
carrier  of  inert  material.* 

Another  modification  of  the  nickel  carbonyl  process  is  described 
by  the  author  f  and  involves  mixing  the  requisite  amount  of  nickel 
carbonyl  with  hydrogen  gas,  or  water  gas,  or  other  gas  suitable  for 
the  purpose  and  then  passing  this  mixture  into  the  oil  to  be  treated. 

The  oil  is  brought  to  the  decomposition  temperature  of  the  nickel  carbonyl 
under  these  circumstances  and  the  metallic  nickel  catalyzer  is  liberated  in  inti- 
mate contact  with  the  hydrogen  gas,  effecting  a  rapid  hydrogenation  of  the  oil. 

*Apparatus  adapted  for  handling  nickel  carbonyl  and  hydrogenating  oils  with  the 
nickel  material  obtained  by  its  decomposition  is  shown  in  U.  S  Patent  to  Ellis, 
1,095,144,  Apr.  28,  1914. 

tU.  S.  Patent  No.  1,154,495,  September  21,  1915. 


•  NICKEL   CARBONYL  239 

The  oil  may  contain,  if  desired,  finely-divided  solid  material  to  serve  as  an 
attaching  base  for  the  separated  nickel.  In  case  the  finely-divided  or  colloidal 
nickel  which  forms  is  not,  after  hydrogenation,  readily  removed  by  filtration, 
the  oil  may  be  boiled  with  an  aqueous  acid  solution  to  remove  such  nickel  mate- 
rial. 

Or  the  oil  may  be  heated  to  about  180°  C.,  and  atomized  with  a  mixture  of 
hydrogen  gas  and  nickel  carbonyl.  The  nickel  carbonyl  may  be  added  to  the  oil 
and  the  mixture  then  atomized  with  hydrogen  gas,  the  temperature  being  regu- 
lated for  the  production  of  the  active  material.  After  such  atomization  the  oil 
may  be  passed  through  a  heated  tube  or  over  a  bed  of  heated  fragmental  mate- 
rial. Also,  the  oil  may  be  mixed  with  a  small  amount  of  nickel  carbonyl  and 
caused  to  flow  downwardly  through  a  tower  containing  baffles  while  hydrogen 
gas  or  other  gas  is  allowed  to  flow  upwardly  against  the  downwardly  flowing 
stream  of  oil.  The  tower  may  be  heated  at  one  or  more  points  so  as  to  secure 
a  temperature  sufficient  to  decompose  the  nickel  carbonyl  and  then,  if  desired, 
the  temperature  may  be  modified  so  that  the  mixture  on  flowing  through  another 
portion  of  the  tower  is  subjected  to  a  temperature  better  adapted  for  the 
hydrogenation  process  proper. 

Nickel  carbonyl  also  may  be  employed  in  a  different  way,  in  that  it  may  be 
mixed  with  asbestos  or  fuller's  earth,  or  other  similar  carrier  and  heated  to  form 
catalytic  nickel  without  resorting  to  direct  reduction  of  say  nickel  oxide  by 
hydrogen.  Such  a  catalytic  body  may  then  be  used  for  treating  oils  in  the 
presence  of  hydrogen  under  suitable  conditions  of  temperature  and  pressure. 

In  the  case  of  oleic  acid  or  other  bodies  which  may  be  converted  into  a 
vapor  form,  the  nickel  carbonyl  and  hydrogen  may  be  mixed  with  the  vapors  of  such 
bodies  and  passed  through  a  heating  zone,  preferably  being  raised  to  a  tempera- 
ture of  180°  or  200°  C.,  or  to  whatever  temperature  under  the  particular  condi- 
tions of  operation  is  required  for  a  satisfactory  decomposition  of  the  carbonyl 
compound  into  an  active  body.  In  this  case  also  nascent  nickel  is  liberated  in 
the  presence  of  hydrogen  to  good  advantage.* 

Lessing  f  uses  nickel  carbonyl  in  the  hydrogenation  of  unsaturated 
substances.  (See  page  42.) 

Fig.  49a  is  a  view  of  a  hydrogenating  apparatus  suggested  by  Lessing  and 
Fig.  496  represents  a  section  of  the  upper  portion  of  the  hydrogenating  vessel 
showing  a  spraying  nozzle  through  which  the  liquid  to  be  treated  may  be  forced. 
A  is  the  vessel  in  which  hydrogenation  occurs.  The  substance  to  be  hydro- 
genated  is  pumped  from  a  supply  tank  through  a  pre-heater  contained  in  a 
tank  C,  into  vessel  A  which  is  heated  by  a  steam  jacket.  The  hydrogenated 
substance  is  forced  by  the  pressure  from  vessel  A  into  the  tank  C  where  it  is 
used  as  heating  agent.  If  finished  it  is  run  off;  if  not  finished,  it  is  returned  by 
the  circuit  shown.  The  gases  enter  on  the  right,  are  compressed  by  compressor 
D,  and  forced  through  the  volatilizer  E,  passing  therein  over  reduced  nickel. 
The  gases  issuing  from  volatilizer  E  and  containing  nickel  carbonyl  then  enter 
vessel  A.  The  gases  left  unabsorbed  and  now  free  from  nickel  issue  from  the 

*  See  also  U.  S.  Patent  to  Ellis,  No.  1,138,201,  May  4,  1915,  and  1,251,202,  Dec. 
25,  1917. 

f  U.  S.  Patent  No.   1,162,623,  November  30,   1915. 


240 


THE  HYDROGENATION  OF  OILS 


vessel  A  through  the  right-hand  outlet  at  the  top  of  A  and  are  passed  through 
cooler  F  and  can  be  either  discharged  or  returned  into  circulation.  Any  oil 
carried  along  with  the  gases  is  deposited  in  the  cooler  F  and  may  be  run  off. 
If  the  compound  to  be  treated  is  in  the  state  of  gas  or  vapor,  as  for  instance, 
in  the  hydrogenation  of  the  more  volatile  tar  oils,  it  is  simply  mixed  with  the 
hydrogen  containing  the  nickel  carbonyl  and  subjected  to  the  temperature  re- 
quired for  hydrogenation.  Likewise  in  the  case  of  a  liquid  some  hydrogen  may 
be  mixed  with  the  liquid,  a  spray  being  then  formed  by  injector  action  instead 
of  by  liquid  pressure. 

Crossley  *  refers  to  British  patent  to  Lessing,  18,998,  of  1912,  and  states  that  the 
process  described  therein  appears  to  differ  materially  from  others,  more  particularly 
in  the  novel  method  for  bringing  catalyst  and  oil  in  contact.  According  to  this 


FIG.  49a. 


FIG.  496. 


process  hydrogen  containing  5  to  10  per  cent  of  carbon  monoxide,  such  as  may  easily 
be  prepared  from  water-gas  or  the  thermal  decomposition  of  coal  gas  or  hydro- 
carbons, is  passed  over  reduced  nickel,  with  formation  of  nickel  carbonyl.  The 
nickel  need  not  be  pure,  but  in  the  form  of  such  complex  mixtures  as  are  obtained 
in  the  treatment  and  reduction  of  nickel  ores.  The  mixture  of  hydrogen  and  any 
desired  proportion  of  nickel  carbonyl  is  then  passed  into  the  substance  to  be  hydro- 
genated  at  a  temperature  between  200°  to  240°  C.  when  the  nickel  carbonyl  is 
decomposed  and  elementary  nickel,  in  a  very  pure  and  particularly  active  form,  is 
produced.  The  proportion  of  nickel  carbonyl  required  is  very  small,  excellent 
results  having  been  obtained  with  an  amount  equivalent  to  0.1  part  of  nickel  in 
per  100  parts  of  oil.  Fresh  nickel  carbonyl  is  always  passing  into  the  substance 
to  be  hydrogenated,  and  the  nickel  is  believed  to  act  in  the  nascent  condition  at 
the  moment  of  decomposition  of  the  nickel  carbonyl.  This  he  states  seems  to  be 
borne  out  by  the  fact  that  if  the  same  percentage  of  nickel  be  introduced  into  an  oil 
as  nickel  carbonyl,  the  latter  decomposed  and  then  hydrogen  passed  in,  there  is 
practically  no  result  from  the  commercial  point  of  view. 

*  Pharm.  Soc.,  Apr.  21,  1914;  Pharm.  J.,  1914,  92,  604,  637  and  676;  J.  S.  C.  I.,  1914, 
1135. 


^ICKEL   CARBONYL  241 

George  Schicht  A.-G.  *  recommends  a  form  of  nickel  kieselguhr 
catalyzer  prepared  from  nickel  carbonyl.  The  carbon  monoxide 
required  may  be  obtained  from  water  gas  by  the  Linde-Caro  process. 

The  catalytic  material  is  prepared  in  the  following  manner:  Carbon  monoxide 
is  conducted  under  pressure  over  finely-divided  nickel  which  is  heated  in  a  retort 
and  the  nickel  carbonyl  which  is  formed  is  cooled  below  its  boiling-point.  Puri- 
fied kieselguhr  is  placed  in  a  nickel  vessel,  the  nickel  carbonyl  is  added  and  the 
mixture  heated  to  cause  metallic  nickel  to  form  by  decomposition  of  the  carbonyl. 
The  carbon  monoxide  liberated  is  removed  and  can  be  used  again  to  form 
nickel  carbonyl.  The  last  traces  of  carbon  monoxide  or  undecomposed  nickel 
carbonyl  which  may  tend  to  effect  the  progress  of  reduction  injuriously  are 
removed  through  treatment  with  hydrogen,  carbon  monoxide  or  other  indif- 
ferent gas.  The  nickel  kieselguhr  material  is  warmed  during  this  stage  of  the 
process.  The  product  is  ground  with  oil  with  exclusion  of  air  affording  an 
"  emulsion  "  or  pasty  composition  which  is  used  as  a  source  of  catalytic  mate- 
rial. In  place  of  oil,  any  suitable  liquid  vehicle  may  be  used.  The  product  is 
stated  to  be  of  such  a  character  that  when  mixed  with  oil  it  does  not  lump  together 
or  deposit  on  the  bottom  of  the  vessel.  The  regeneration  of  spent  catalyzer  is 
simple,  for,  after  the  removal  of  the  oil,  it  is  stated  that  the  nickel  may  be 
again  directly  converted  into  nickel  carbonyl  and  decomposed  as  before.  The 
residue  of  kieselguhr  from  which  the  nickel  has  been  removed  as  the  carbonyl 
may  likewise  be  utilized  as  a  carrier. 

In  a  publication  by  Coleman  entitled  "  The  Nickel  Industry " 
issued  by  the  Canadian  Department  of  Mines,  1913,  153,  a  very 
complete  description  of  operation  of  the  nickel  carbonyl  process 
for  producing  nickel,  as  carried  out  at  the  Mond  plant,  Clydach, 
Wales,  is  given. 

*  Austrian  Patent  No.  70,771;    Seifen.  Ztg.,  1916,  169. 


CHAPTER    X 
THE   RARE   METALS   AS   CATALYZERS 

As  a  catalyzer  in  this  field  palladium  has  received  considerable 
study,  for,  in  spite  of  high  first  cost,  its  pronounced  effectiveness, 
together  with  its  ability  to  effect  hydrogenation  at  relatively  low 
temperatures,  makes  it  particularly  attractive. 

Many  years  ago,  Fokin  *  stated  that  he  regarded  palladium  as  the 
most  powerful  of  all  catalyzers,  having  found  that  reduction  takes 
place  readily  at  80°  to  90°  C.,  while  with  nickel,  a  temperature  of  180° 
to  200°  C.  was  necessary  for  practical  hydrogenation.  Fokin's  experi- 
ments at  that  time  were  concerned  with  electrolytic  reduction.  By 
this  means  he  reduced  linseed,  wood,  castor  and  cod  liver  oil.  He 
found  that  while  palladium  black  would  reduce  oleic  acid  completely 
to  stearic  acid,  platinum  black  under  the  same  conditions  gave  only 
24  per  cent  of  stearic  acid. 

Paal  j  worked  with  colloidal  palladium  preparations  and  hydro- 
genated  castor,  olive,  fish  oil  and  animal  fats.  He  found  that  sesame 
oil,  after  hydrogenation,  showed  the  Baudoin  reaction  only  very 
faintly,  while  cottonseed  oil  no  longer  responded  to  the  Becchi  and 
Halphen  reaction.  Skita  has  worked  with  palladium  incorporated 
with  a  protective  colloid. 

Paal  recommends  {  platinum  or  palladium  chloride  admixed  with  a 
neutralizing  agent  such  as  sodium  carbonate.  He  states  that  the 
reduction  of  fats  and  unsaturated  fatty  acids  of  animal  and  vegetable 
origin  may  be  effected  by  allowing  hydrogen  to  act  on  these,  in  presence 
of  platinum  metals,  or  protohydroxide  compounds  of  the  latter,  which 
have  been  deposited  upon  certain  finely-divided  substances  and  act  as 
catalyzers  or  carriers  of  hydrogen.  It  has  also  been  ascertained  that 
the  reduction  of  the  fats  and  fatty  acids  may  be  effected  by  hydrogen 
in  presence  of  solid  salts  of  the  platinum  metals.  Both  the  simple 
salts,  such  as  palladium  protochioride  (PdCl2),  platinum  protochloride 
(PtCl2),  platinum  chloride  (PtCl4),  platinum  hydrochloride  (H2PtCl6), 
platinum  sulfate  and  the  double  salts,  for  instance  potassium 

*  Chem.  Ztg.  [2],  1906,  758;  [1],  1907,  324. 
t  Ber.,  41,  2282. 

t  U.  S.  Patent  1,023,753,  April  16,  1912. 
242 


THE  RARE  METALS  AS  CATALYZERS  243 

! 

chloroplatinate  (K2PtCl6),  copper  platinochloridc,  may  be  used. 
When  the  double  ,s.alts  are  used,  care  must  be  taken  that  no  anticata- 
lytic  substances,  sucli  for  instance  as  lead,  find  their  way  into  the 
reduction  mixture.  Use  may  be  made  of  salts  whose  acid  radicals  or 
other  constituents  are  themselves  reduced  by  hydrogen,  for  example 
acid  platinous  oxalate.  In  all  cases  the  method  is  simple;  and  it  is 
distinguished  from  those  in  which  the  finely-divided  metals  are  used 
by  the  omission  of  the  preparation  of  the  finely-divided  platinum 
metals  or  their  protohydroxides  and  of  the  deposition  on  special 

carriers. 

> 

The  salts  in  a  crushed  condition,  preferably  in  the  state  of  powder,  are  mixed 
with  the  fats  or  fatty  acids  to  be  hydrogenated;  and  hydrogen  is  allowed  to  act  on 
this  mixture,  with  stirring,  at  temperatures  below  100  degrees  preferably  under  a 
pressure  of  several  atmospheres.  In  a  short  time  the  solid  reduction  product  of  the 
fat  or  fatty  acid  will  be  obtained.  All  that  is  necessary  to  insure  the  action  of  the 
solid  salts  of  the  platinum  metals  is  that  they  must  be  present  in  the  solid  form 
during  the  progress  of  the  reaction.  The  salts  may  also  be  added  to  the  fats  in  a 
dissolved  condition  (for  example  in  aqueous  solution),  the  solvent  being  evaporated 
before  or  at  the  beginning  of  the  reduction  process.  A  suspension  of  the  solid  salts 
may  also  be  used.  For  example,  the  salts  of  the  platinum  metals  may  be  triturated 
with  a  portion  of  the  fat  or  oil  that  is  to  be  reduced,  the  mixture  being  then  added 
to  the  main  portion  of  the  fats  or  fatty  acids  to  be  reduced.  Or  a  suspension  of 
the  salts  in  mineral  oil  may  be  prepared,  and  this  mixture  may  be  added  to  the  sub- 
stances that  are  to  be  reduced,  in  which  case  the  suspensory  medium  may  be  elimi- 
nated during  the  process  of  reduction.  A  single  salt  of  a  platinum  metal  may  be 
used,  or  several  salts,  and  even  several  platinum  metals  may  be  mixed  together; 
and  the  salts  may  also  be  used  in  conjunction  with  the  platinum  metals  which  have 
been  deposited  on  carriers,  devoid  of  anticatalytic  action,  such  as  copper,  or  mag- 
nesium carbonate.  It  is  probable  that,  during  the  process,  the  salts  of  the  platinum 
metals  are  split  up  into  metal  and  free  acid,  for  example: 

PdCl2  +  H2  =  Pd  +  2  HC1. 

In  any  case,  however,  the  solid  platinum  metal  salts  greatly  facilitate  the  absorp- 
tion of  hydrogen  by  fats  and  fatty  acids.  Very  small  quantities  of  the  platinum- 
metal  salts  are  sufficient  to  reduce  large  quantities  of  fat  or  fatty  acids  in  presence 
of  hydrogen.  When  the  reduction  process  is  completed,  the  platinum  metals  or 
their  compounds  can  be  easily  separated  from  the  reduced  fat  or  fatty  acid  by  filtra- 
tion, and  used  again. 

To  prevent  the  formation  of  free  acid,  as,  for  example,  hydrochloric  acid  from  the 
chlorides  of  the  platinum  metals,  in  the  reducing  process,  there  is  added  to  the 
powdered  platinum  salt  a  neutralizing  agent,  such  as  anhydrous  soda,  in  sufficient 
quantity  to  combine  with  the  liberated  acid.  The  employment  of  salts  of  the 
platinum  metals  assists  the  reduction  process  considerably  more  than  is  done  by 
palladium  black 'or  platinum  black  containing  an  amount  of  platinum  metal  equal 
to  that  in  the  platinum  metal  salts  used  in  the  present  method.  Thus,  for  example, 
1.7  parts  of  PdCl2  ( =  1  part  of  Pd)  in  presence  of  hydrogen  will  convert  10,000  parts 
of  fat  or  fatty  acid  into  solid  masses  within  3  or  4  hours.  If,  however,  the  PdCl2  be 


244  THE  HYDROGENATION   OF  OILS 

replaced  by  a  quantity  of  palladium  black  containing  the  same  amount  of  palladium, 
then,  with  a  ratio  of  1  part  of  Pd  to  10,000  parts  of  fat  or  fatty  acid,  these  substances, 
according  to  Paal,  will  remain  liquid,  even  when  the  palladium  and  hydrogen  are 
allowed  to  act  for  twice  or  three  times  as  long  as  with  PdCla. 

Paal  notes  that  the  time  required  for  the  reduction  depends  on  the  amount  of 
the  platinum  metal  salt  used,  and  on  the  pressure  under  which  the  hydrogen  is 
allowed  to  act.  By  using  a  palladium  salt  as  the  hydrogen  carrier,  about  50,000 
parts  of  fat  or  unsaturated  fatty  acid  can  be  hydrogenated  within  from  6  to  8  hours 
with  a  quantity  of  salt,  for  example,  PdCl2,  corresponding  with  1  part  of  Pd. 

Paal  gives  the  following  example:  One  million  parts  by  weight  of  castor  oil  or 
oleic  acid  are  treated  with  thirty-four  parts  by  weight  of  dry  palladium  protochloride 
( =  20  parts  of  Pd)  in  the  form  of  powder,  with  or  without  the  equivalent  amount  of 
anhydrous  soda;  or  w^th  140  parts  by  weight  of  dry  platinum  protochloride  ( =  100 
parts  of  Pt)  in  the  form  of  powder;  or  172  parts  of  platinum  chloride;  or  230  parts 
of  platinum  hydrochloride,  with  or  without  addition  of  an  equivalent  amount  of 
anhydrous  soda.  The  mixture  is  placed  in  $  pressure  vessel,  from  which  the  air 
is  exhausted  as  completely  as  possible,  and  hydrogen  is  then  admitted  into  the 
vessel  under  a  pressure  of  2  to  3  atmospheres.  The  reduction  mixture  is  kept  in 
motion  by  a  stirring  apparatus.  The  vessel  is  heated  to  about  80°  C.  although  the 
reduction  may  also  be  carried  out  at  a  lower  temperature.  The  progress  of  the 
reduction  and  the  consumption  of  hydrogen  is  revealed  by  the  fall  in  pressure  as 
indicated  by  the  pressure  gauge.  When  the  gauge  registers  only  a  low  pressure, 
a  fresh  quantity  of  hydrogen  is  admitted.  The  completion  of  the  reduction  process 
can  be  recognized  by  the  gas  pressure  remaining  constant  for  some  considerable 
time.  When  the  reduction  is  ended,  the  reduction  product  is  freed  from  the  catalyzer 
in  a  filter  press  which  is  adapted  to  be  heated. 

The  work  in  the  field  of  catalytic  reduction  of  organic  compounds 
has  been  rather  comprehensively  covered  in  a  publication  by  Skita 
entitled  "  Uber  Katalytische  Reduktionen  Organischer  Verbindungen 
(Stuttgart,  1912).  Skita  has  taken  out  a  patent  assigned  to  Boeh- 
ringer  and  Son  *  which  is  concerned  with  the  hydrogenation  of  organic 
compounds  with  the  aid  of  catalyzers  consisting  of  salts  of  the  plati- 
num group  of  metals.  The  protective  colloid  previously  employed 
he  now  finds  to  be  unnecessary.  He  states  he  has  found  that  an  un- 
saturated substance  can  be  hydrogenated  when  there  is  added  to  it, 
or  its  solution  or  suspension,  a  small  amount  of  palladium  chloride 
or  any  other  soluble  salt  of  a  platinum  metal  and  the  whole  exposed 
to  hydrogen,  most  advantageously  under  pressure.  The  addition  of 
an  acid  is  usually  advantageous  in  this  operation  and  hydrochloric 
acid  is  recommended;  but  with  fatty  bodies  it  suffices  merely  to  add  a 
simple  aqueous  solution  of  a  compound  of  a  metal  of  the  platinum 
group.  As  an  example,  he  states,  that  50  grams  of  olive  oil  may  be 
suspended  in  a  solution  containing  about  0.05  gram  of  platinum 
chloride,  20  cc.  of  alcohol,  50  cc.  of  water  and  8  cc.  of  dilute  hydro- 

*  U.  S.  Patent  1,063,746,  June  3,  1913. 


THE  RARE  METALS  AS  CATALYZERS  245 

chloric  acid.  After  treatment  with  hydrogen  at  a  pressure  of  about 
4  atmospheres  and  at  a  temperature  of  70°  C.  a  solid  fat  results. 
In  another  example  about  250  grams  of  castor  oil  is  well  mixed 
with  a  solution  of  about  0.05  gram  of  palladium  chloride  in  5  cc.  of 
water.  The  whole  may  then  be  treated  at  about  70°  C.  in  an  auto- 
clave with  constant  stirring,  with  hydrogen  under  ^  pressure  of  4 
atmospheres.  After  two  and  one-half  hours  the  oil  will  be  found  so 
far  hydrogenated  that  it  will  solidify  to  a  hard  mass  on  cooling.* 

In  an  address  before  the  Chemical  Society  of  Karlsruhe  Dr.  Skita 
made  the  following  comments  on  the  hydrogenation  of  organic 
material.f 

He  stated  that  the  acceleration  which  various  reactions  experience 
in  the  presence  of  catalyzer  is  the  more  rapid  the  greater  the  surface 
of  the  catalyzer.  As  a  result  a  catalyzer  in  solution  is  alwa}^s  more 
active  than  is  the  case  when  the  catalyzer  is  in  a  finely-divided  or  pre- 
cipitated state.  This  especially  is  true  with  metals  of  the  platinum 
group  which  exert  an  action  of  a  very  marked  character  when  in  solu- 
tion in  the  colloidal  condition. 

Colloidal  platinum  was  first 'produced  by  Bredig  by  the  action  of  an 
electric  current  on  metallic  platinum  in  aqueous  or  ethereal  solution. 
Bredig  recognized  the  property  which  these  colloidal  solutions  pos- 
sessed of  serving  as  a  carrier  for  hydrogen  and  he  in  fact  reduced 
nitrous  acid  to  ammonia.  Such  colloids  are  not  reversible,  that  is  to 
say  if  the  colloidal  solution  is  evaporated  to  dryness  the  metal  will 
not  again  go  into  solution.  A  metal  colloid  which  is  easily  soluble  in 
water  was  discovered  by  Paal  who  made  use  of  a  water-soluble  pro- 
tective colloid,  namely,  the  sodium  salts  of  protalbinic  or  lysalbinic 

*  The  hydrogenation  of  unsaturated  substances  is  effected,  according  to  Skita, 
by  treatment  with  hydrogen  in  the  presence  of  small  quantities  of  compounds  of 
metals  of  the  platinum  group  in  solution.  The  substances  to  be  hydrogenated  may 
be  dissolved  or  suspended  in  a  liquid  (French  Patent  447,420,  Aug.  20,  1912;  also 
British  Patent  28,754,  Aug.,  1912,  and  addition  to  the  latter  Patent  18,996  (1912). 
A  solution  of  palladium  chloride  acidulated  with  dilute  hydrochloric  acid  was 
used  by  Skita  as  a  catalytic  solution  for  the  treatment  of  camphene.  Hydrogen  was 
used  under  a  pressure  of  one  atmosphere.  The  hydrogenation  of  olive  and  castor 
oil  in  this  manner  is  described.  In  the  addition  patent  Skita  states  that  the  employ- 
ment of  dilute  acid  is  not  always  necessary  since  in  many  cases  the  reaction  can  be 
carried  out  simply  by  passing  hydrogen  through  a  mixture  of  the  substances  to  be 
reduced  and  a  solution  of  the  salt.  J.  S.  C.  I.,  March  15,  1913,  253. 

Skita  (Chem.  Zeit.  Rep.  (1913),  680;  British  Patents  18,996,  1912,  and  16,283, 
1913)  carries  on  reduction  processes  without  the  addition  of  any  acid  to  a  solu- 
tion of  a  salt  of  the  platinum  group  and  also  makes  use  of  colloidal  solutions  of  an 
hydroxide  of  the  platinum  group  as  a  catalyzer. 

t  Seifen.  Ztg.  (1913),  960. 


246  THE  HYDROGENATION  OF  OILS 

acids,  to  maintain  the  metallic  platinum  or  palladium  in  a  water- 
soluble  condition.* 

With  colloids  of  this  character  prepared  from  palladium  Paal  suc- 
ceeded in  adding  hydrogen  to  a  large  number  of  unsaturated  aliphatic 
compounds  which  were  soluble  in  water  or  dilute  alcohol.  For  the 
reduction  of  many  organic  compounds,  such  as  acids,  bases  and  hydro- 
carbons, the  presence  of  acid  material  is  of  importance  and  accordingly 
Skita  has  used  an  acid-stable  protective  colloid  such  as  gum  arabic  in 
.place  of  the  sodium  salts  mentioned  above.  If  gum  arabic  is  added 
to  a  solution  of  platinum  chloride,  no  platinum  hydroxide  is  precipi- 
tated when  carbonate  of  soda  is  added  to  the  solution,  for  the  platinum 
remains  suspended  in  the  colloidal  condition. 

By  careful  evaporation  platinum  compounds  may  be  obtained  as 
black  plates  or  scales  which  are  soluble  in  water  and  dilute  acids. 
When  these  colloidal  solutions  of  the  hydroxide  are  agitated  in  the 
presence  of  hydrogen  a  very  acid-resistant  form  of  colloidal  platinum 
results.  On  evaporation  a  form  of  platinum  is  obtained  which  is 
easily  soluble  in  water.  All  such  platinum  and  palladium  compounds 
are  eminently  adapted  to  catalytically  transfer  hydrogen  to  unsatu- 
rated material  contained  in  an  acid  or  neutral  vehicle.  It  is  especially 
easy  to  add  hydrogen  to  the  double  bonds  of  aliphatic  and  hydrocyclic 
hydrocarbon  compounds.  This  is  the  case  as  regards  the  reduction 
of  alkaloids. 

Another  interesting  observation  is  that  very  stable  colloidal  solu- 
tions of  platinum  may  be  obtained  readily  by  passing  hydrogen 
through  such  colloidal  solutions  of  platinum  containing  gum  arabic, 
even  when  the  solution  is  cold.  In  a  similar  manner  colloidal  solu- 
tions of  palladium  are  produced  from  palladium  chloride. 

Finally  it  may  be  mentioned  that  in  this  way  hydrogen  may  be 
added  to  aromatic  and  heterocyclic  compounds  which  cannot  be 
hydrogenated  with  platinum  black  catalyzer. f 

*  Colloidal  solutions  of  gold,  silver,  platinum,  palladium,  copper,  lead,  iron,  zinc, 
tin,  nickel,  aluminum,  magnesium,  bismuth,  antimony  and  cadmium,  respectively, 
have  been  prepared  with  great  ease  by  an  electrical  disintegration  method,  using 
a  high-frequency  alternating  arc,  the  leads  to  which  were  taken  from  two  points 
on  the  inductance  of  the  oscillatory  circuit  of  a  Poulsen  arc  as  used  in  wireless  teleg- 
raphy. By  varying  the  conditions  it  was  possible  to  obtain  currents  of  from  0.14 
to  15  amperes  and  E.M.F.  of  480  to  4080  volts,  and  colloidal  solutions  showing 
a  wide  range  of  colors  were  thus  obtained  from  a  number  of  the  metals.  (Morris- 
Airey  and  Long,  Proc.  Univ.  Durham  Phil.  Soc.  (1912-1913),  5,  68;  J.  S.  C.  I.  (1913), 
1015.) 

t  In  his  dissertation  entitled  "Tiber  katalytische  Hydrierungen  organischer  Ver- 
bindungen  mit  kolloidem  Palladium  und  Platin,"  Meyer  draws  the  following  con- 


THE  RARE  METALS  AS  CATALYZERS        247 

Colloidal  suspensions  of  the  metals  *  have  proved  excellent  cata- 
lyzers, effecting  many  of  the  reactions  which  are  brought  about  by 
enzymes.  The  analogy  between  the  action  of  the  finely-divided  metals 
and  the  organic  enzymes  is  strikingly  illustrated  by  the  behavior  of 
poisons  on  the  two.  The  same  substances  which  poison  the  ferments 
and  which  retard  the  rate  at  which  they  decompose  hydrogen  dioxide, 
also  poison  platinum  and  retard  the  rate  at  which  it  effects  the  same 
decomposition.  Thus  mercuric  chloride  and  hydrocyanic  acid  in 
the  merest  traces  poison  the  organic  enzymes.  The  same  quantities 
produce  almost  exactly  the  same  effect  on  the  finely-divided  metals, 
with  respect  to  their  power  to  decompose  hydrogen  dioxide,  f 

elusions.  Methods  of  reduction  depending  on  the  use  of  a  solution  of  palladious 
chloride  and  gum  arabic  in  water-alcohol  mixture,  forming  colloidal  palladium  with 
hydrogen,  do  not  progress  satisfactorily  unless  bodies  are  present  which  are  capable 
of  forming  addition  compounds  with  palladious  chloride.  The  action  of  hydrogen 
on  a  hot  solution  of  palladium  chloride  and  a  protective  colloid  gives  rise  to  a  colloidal 
solution  of  palladium.  From  colloidal  palladium  or  platinum  solutions  using  gum 
arabic  or  gelatine  as  a  protective  colloid,  the  corresponding  reversible  metal  colloid 
is  obtained.  With  the  aid  of  gum  arabic  or  gelatine  as  a  protective  colloid  it  is 
possible  to  obtain  permanent  colloidal  solutions  of  palladium  and  platinum  hydrox- 
ide. By  careful  evaporation  and  drying  of  these  colloidal  solutions  solid  products 
are  obtained  which  may  be  brought  again  into  colloidal  solution  by  peptization. 
Stable  colloid  solutions  of  palladium  may  be  advantageously  obtained  by  the  reduc- 
tion of  dialyzed  colloid  palladious  hydroxide  solutions.  For  the  production  of  a 
colloidal  solution  of  platinum  it  is  recommended  that  reduction  of  chlorplatinic  acid 
by  hydrogen  in  the  presence  of  a  protective  colloid  be  employed,  in  which  case  the 
mixture  should  first  be  inoculated  with  small  amounts  of  colloidal  platinum  or 
palladium.  Colloidal  solutions  of  platinum  and  palladium  with  gum  arabic  or 
gelatine  as  a  protective  colloid  are  well  adapted  to  the  hydrogenation  of  olefine 
bodies.  The  hydrogenation  of  aromatic  bodies  with  colloidal  metallic  platinum  is 
possible  only  in  strong  acetic  acid  solutions.  The  hydrogenation  of  aromatic  bodies 
is  carried  out  more  easily  with  platinum  than  with  palladium.  While  gum  arabic 
is  suitable  for  use  as  a  protective  colloid  with  platinum  or  palladium  in  the  hydro- 
genation of  certain  organic  bodies,  it  is  found  that  gelatine  under  some  conditions 
acts  as  a  catalyzer  poison.  Vulcanized  rubber  also  affects  the  activity  of  the  cata- 
lyzer. The  inoculation  method  for  the  production  of  colloidal  solutions  of  platinum 
affords  a  convenient  laboratory  procedure  for  the  hydrogenation  of  aromatic  bodies 
as  the  formation  of  the  colloidal  solution  and  the  process  of  hydrogenation  follow 
one  another  quickly.  The  hydrogenation  of  aromatic  bodies  using  colloidal  platinum 
as  a  catalyzer  progresses  three  or  four  times  quicker  than  when  platinum  black  is 
employed.  See  also  J.  S.  C.  I.  (1913),  46,  and  Ber.  (1912),  45,  3379. 

A  solution  of  colloidal  platinum  is  capable  of  causing  the  union  of  hydrogen  and 
oxygen.  (Ernst,  Zeitsch.  physikal.  Chem.  (1901),  37,  448.)  Ethylene  unites  with 
hydrogen  even  in  the  cold,  in  the  presence  of  platinum  sponge.  (De  Wilde,  Ber.  7, 
354.) 

*  Jones,  A  New  Era  in  Chemistry. 

f  Measurements  have  shown  that  the  decomposition  of  hydrogen  dioxide  by  metals 


248  THE  HYDROGENATION  OF  OILS 

Karl  *  has  studied  with  considerable  care  and  in  a  quantitative  way 
the  action  of  palladium  supported  on  various  bodies.  He  found  that 
palladium  precipitated  on  finely-divided  nickel  or  magnesium  proved 
effective  catalytically,  while  if  precipitated  on  lead,  aluminum,  iron, 
or  zinc,  little  or  no  hydrogenation  was  effected,  owing  to  the  anti- 
catalytic  action  of  these  metals.  While  metallic  zinc  is  anticatalytic, 
zinc  oxide  and  carbonate  have  no  such  effect.  In  these  investigations 
Karl  worked  principally  with  fish,  cotton  and  castor  oil  and  oleic  acid.f 

is  a  reaction  of  the  first  order,  that  is,  the  metal,  strictly  speaking,  does  not  enter  into 
the  reaction  at  all,  only  the  mass  of  hydrogen  dioxide  present  undergoing  change. 

A  hydrogenizing  ferment  in  the  animal  organism  capable  of  transforming  nitro- 
benzene into  aniline  has  been  observed  by  Abelous  and  Gerard  (Comptes  Rend., 
130  (7),  420).  A  clear  aqueous  extract  of  horse's  liver,  in  presence  of  chloroform 
and  in  an  atmosphere  of  hydrogen,  reduced  nitrobenzene  to  aniline,  while  the  same 
extract,  previously  boiled,  was  without  action.  Abelous  and  Gerard  have  previously 
shown  (J.  S.  C.  I.,  1899,  871)  the  deoxidizing  action  of  this  ferment,  but  have  had 
no  instance  of  hydrogenation  under  its  influence.  (See  also  Chandler,  J.  S.  C.  I., 
1913,  73.) 

*  Inaugural  Dissertation,  Erlangen,  1911. 

t  Paal  and  Karl  (Ber.  (1913),  3069;  Chem.  Ztg.  Rep.  (1913),  642)  tested  palla- 
dium on  various  carriers  as  catalytic  material  for  hardening  fats  and  have  found 
that  the  oxides,  hydroxides  and  carbonates  of  lead,  cadmium,  zinc,  aluminum  and 
iron  have  an  anti-catalytic  action  similar  to  the  metals  which  they  contain.  The 
corresponding  compounds  of  nickel  and  cobalt,  and  also  magnesium  oxide,  were  in- 
vestigated. These  carriers  were  coated  with  palladium  by  mixing  with  a  solution 
of  palladium  chloride  in  a  weak  aqueous  solution  of  hydrochloric  acid  at  room  temper- 
ature, or  slightly  warmed.  Palladious  hydroxide  was  thus  precipitated  and  reduc- 
tion was  obtained  by  treatment  of  the  powder,  which  was  first  moistened  with 
ether,  to  the  action  of  hydrogen  at  room  temperature.  The  catalyzer  was  mixed 
with  fatty  material  without  permitting  contact  with  the  air  and  reduction  was 
carried  out  in  an  agitator  in  an  atmosphere  of  hydrogen.  Magnesium  oxide  did 
not  retard  the  catalytic  action  of  palladium.  In  fact,  the  reduction  process  appeared 
to  be  somewhat  increased  by  the  presence  of  this  material. 

Paal  and  Windisch  carried  on  similar  experiments  with  platinum.  (Ber.  (1913), 
4010.)  Metal  powders  of  various  sorts  were  purified  with  alcohol  and  ether  and  then 
platinized  by  shaking  with  a  solution  of  chlorplatinic  acid.  Metallic  oxides  and 
carbonates  were  platinized  by  the  action  of  sodium  carbonate  and  hydrazine  hy- 
drate on  a  solution  of  chlorplatinic  acid  containing  the  oxide  or  carbonate  in  suspen- 
sion. These  products  as  catalyzers  in  the  hydrogenation  of  cottonseed  oil  were 
found  to  have  differing  degrees  of  catalytic  action,  and  only  nickel  and  magnesium 
had  no  influence  on  the  activity  of  the  platinum.  The  platinum  was  much  less 
active  in  the  presence  of  aluminum,  cobalt  and  bismuth,  and  was  rendered  completely 
inactive  by  iron,  copper,  zinc,  silver,  tin  and  lead.  Of  the  oxides  and  carbonates 
examined,  only  the  magnesium  compounds  were  without  influence. 

Wieland  (Ber.  (1912),  45,  2615)  considers  palladium  black  less  sensitive  to 
"poisons"  than  platinum  black,  for  in  presence  of  the  former  a  sample  of  benzene 
containing  thiophen  absorbed  hydrogen  at  a  noticeable  rate  although  not  so  rapidly 
as  pure  benzene. 


THE  RARE  METALS  AS  CATALYZERS  249, 

A  long  list  of  salts  available  as  catalyzers  is  given  in  German  Patent 
260,885  *  embracing  the  sulfates,  nitrates  and  chlorides  of  platinum 
and  palladium,  and  double  salts  of  these  with  alkali  chlorides  and 
other  chlorides,  also  certain  complex  compounds  of  these  metals. 
The  salts  are  added  in  an  undissolved  state  directly  to  the  oil  to  be 
hardened  and  subsequently  a  neutralizing  agent  also  undissolved  is 
added.  The  temperature  is  maintained  below  100°  C.  When  em- 
ploying double  salts  care  should  be  taken  to  have  no  anticatalytic 
substances,  such  as  lead,  present  in  the  mixture.  Salts,  such  as  acid 
oxalate  of  platinum,  whose  acid  radical  is  capable  of  reduction,  may 
be  used.f  If  necessary,  a  solid  neutralizing  agent  may  be  added  (cf. 
Paal). 

The  Seifenscider  Zeitung,  1912,  550,  makes  mention  of  a  German 
Patent  application  for  a  process  of  making  hardened  fats,  using  as 
catalyzers  platinum  and  platinum  hydroxide  in  the  form  of  precipi- 
tates and  on  inert  carriers  in  place  of  the  corresponding  compounds  of 
palladium. 

In  order  to  avoid  the  accidental  introduction  of  air  or  mercury  when  reducing 
by  means  of  hydrogen  and  colloidal  platinum  a  special  apparatus  has  been  constructed 
by  Stark  (Ber.  1913  (46),  2335).  It  consists  of  a  glass  vessel  with  two  necks,  each 
provided  with  a  glass  stopcock.  A  small  funnel  with  a  stopcock  is  fused  into  the 
upper  part  of  the  vessel  between  the  two  necks.  One  neck  is  connected  with  the 
source  of  hydrogen,  the  other  with  a  graduated  gas  burette  and  mercury  reservoir. 
The  substance  to  be  reduced  is  placed  in  the  glass  vessel  and  a  current  of  hydrogen 
passed  through.  At  this  stage  the  burette  and  reservoir  contain  no  mercury.  The 
hydrogen  supply  is  then  cut  off  and  mercury  is  poured  into  the  reservoir  from  which 
it  flows  and  partly  fills  the  burette.  By  lowering  the  reservoir  a  solution  of  platinum 
or  palladium  can  be  introduced  through  the  funnel  with  the  stopcock  without  ad- 
mitting any  air. 

Lehmann  carries  out  the  hydrogenation  of  oils  or  unsaturated  fatty 
acids  by  passing  hydrogen  through  oil  containing  a  small  amount  of 
osmium  tetroxide,  while  the  oil  is  being  heated.  Osmium  dioxide 
forms  from  the  tetroxide,  producing  a  colloidal  solution  which  can  be 
removed  by  animal  charcoal.  In  one  experiment  10  grams  olive  oil 

Cf.  Windisch,  Ueber  die  Hydrogenisation  ungesattigtcr  organischer  Verbindun- 
gen  durch  Platin  und  Palladium-wasserstoff  und  die  antikatalytischc  Wirkung  von 
Fremdstoffen  auf  den  Hydrogenisierungsprozess.  Erlangen,  1913. 

Dissertation:  Schwarz,  Erlangen,  1913,  publishes  work  on  colloidal  platinum 
and  the  effect  of  anti-catalytic  bodies.  J.  v.  Bergen,  Karlsruhe,  1913,  gives  results 
of  work  with  palladium  hydrosols. 

*  Seifen.  Ztg.,  1913,  851. 

t  Fokin  has  used  the  compound  PdCh.2  NaCl  as  a  catalyzer  (Russian  Patent 
22,629,  Sept.  30,  1912;  Chem.  Ztg.  Rep.,  1914,  40). 


250  THE  HYDROGENATION  OF  OILS 

with  0.05  gram  osmium  tetroxide  produced  in  1J  hours  a  fat  of  melting 
point  39°  C.  It  is  not  necessary  to  use  hydrogen  under  pressure.* 

Besides  palladium  and  platinum  the  metals  iridium,  rhodium, 
ruthenium  and  osmium  are  specified  as  catalytic  material.!  Madina- 
veitial  has  studied  the  catalytic  activity  of  ruthenium,  rhodium,  iridium 
and  osmium  black. 

In  connection  with  the  volumetric  determination  of  hydrogen  by 
catalytic  absorption  in  a  solution  of  sodium  picrate  and  colloidal  pal- 
ladium Paal  and  Hartmann  §  note  that  oxygen  and  unsaturated  hydro- 
carbons must  be  removed,  for  in  presence  of  palladium,  hydrogen 
reacts  with  them  to  form  water  and  paraffin  hydrocarbons  respectively; 
and  carbon  monoxide  should  also  be  removed,  as  it  acts  as  a  "  poison  " 
on  the  catalyst,  and  greatly  retards  the  absorption. 

Colloidal  solutions  of  hydroxides  of  metals  of  the  platinum  group,  obtained  by 
treating  a  solution  of  a  salt  of  the  metal  with  sodium  carbonate  in  presence  of  gum 
arabic,  are  found  by  Skita  (British  Patent  16,283,  July  15,  1913)  to  be  efficient  hydro- 
gen carriers  in  the  hydrogenation  of  unsaturated  compounds,  the  reaction  being 
possible  even  in  neutral  solutions.  In  this  manner  it  is  stated  that  unsaturated 
fatty  acids  or  fats  can  be  hydrogenated  to  any  degree.  For  example,  a  hard  fat 
is  obtained  by  passing  hydrogen  at  a  pressure  of  seven  atmospheres  into  a  mixture 
of  50  parts  (by  weight)  of  peanut  oil  and  60  parts  of  a  colloidal  solution  of  palla- 
dious  hydroxide,  containing  about  0.07  part  of  the  hydroxide,  at  a  temperature  of 
60°  C. 

*  Arch.  Pharm.  (1913),  152;  Seifen.  Ztg.  (1913),  418. 

t  Vereinigte  Chemische  Werke  A.  G.  French  Patent  425,729  (1911);  Seifen.  Ztg. 
(1912),  390. 

In  using  platinum  or  palladium  the  following  example  is  given:  1000  kilos  castor 
oil  are  mixed  with  1  kilo  of  catalyzer  which  contains  1  per  cent  of  palladium  or 
2  per  cent  platinum  either  in  the  metallic  state  or  in  the  form  of  the  lower  hydroxide. 
This  mixture  of  oil  and  catalyzer  is  placed  in  a  closed  receptacle  equipped  with  an 
agitator.  Any  moisture  present  is  removed  as  completely  as  possible  and  then 
hydrogen  is  introduced,  creating  a  gas  pressure  of  2  to  3  atmospheres.  The  contents 
of  the  receptacle  are  heated  to  80°  C.  and  the  agitator  put  into  operation.  Hydro- 
gen is  introduced  as  required.  The  hydrogenation  of  fatty  acids  may  be  carried 
out  in  a  similar  manner,  but  care  should  be  taken  to  use  catalytic  material  contain- 
ing palladium  or  platinum  which  is  not  attacked  by  acids.  One  composition  men- 
tioned for  the  purpose  is  prepared  by  mixing  barium  chloride  with  palladium  or 
platinum  chloride  to  which  is  added  sodium  sulfate  and  some  hydroxylaminc  or 
other  reducing  agent.  For  the  production  of  oleic  acid  one  part  of  catalyzer  carry- 
ing 1  per  cent  of  palladium  or  2  per  cent  platinum  is  used  to  1000  parts  of  the  fatty 
acid. 

Palladium  in  various  metallic  forms  as  a  catalyzer  is  mentioned  in  Seifen.  Ztg. 
(1914),  7,  as  forming  a  basis  of  a  patent  application  by  the  Naamlooze  Vennootschap 
Ant.  Jurgens  Vereenigde  Fabrieken.  See  German  Patent  272,340,  1912. 

t  Chem.  Abs.,  1914,  1106. 

§  Ber.  (1910),  43,  243, 


THE  RARE  METALS  AS  CATALYZERS  251 

Thron  *  adds  hydrogen  to  unsaturated  bodies  with  the  aid  of  a 
finely-divided  metal  of  the  platinum  group  and  formic  acid.  The 
latter  is  split  by  the  platinum  metals  by  catalytic  action  into  carbonic 
acid  and  hydrogen,  the  latter,  it  is  stated,  causing  the  formation  of  a 
compound  of  the  platinum  metal  and  hydrogen  (hydride  of  the  plati- 
num metal).  By  adding  to  the  substance  to  be  hydrogenized  formic 
acid  and,  for  example,  palladium  black,  the  development  of  carbonic 
acid  begins  at  once,  while  hydrogen  is  combined  with  the  unsaturated 
bodies  present. 

A  platinum  catalyzer  used  by  Porter  (U.  S.  Patent  684,863,  Oct.  22,  1901)  for 
igniting  combustible  gas  is  prepared  by  mixing  platinum  black  with  the  oxide  of 
zirconium  in  about  the  proportion  of  twenty-five  per  cent  of  platinum  to  seventy- 
five  per  cent  of  zirconium  oxide.  To  prepare  this,  the  platinum  in  a  state  of  solu- 
tion is  mixed  with  the  oxide  of  zirconium  and  the  liquid  is  evaporated,  leaving  the 
platinum  compound  distributed  throughout  the  mass.  This  is  then  applied  to  some 
incombustible  substance,  such  as  asbestos  or  mineral  wool,  which  forms  a  convenient 
support  for  the  substance.  After  heating,  the  platinum  remains  in  a  finely-divided 
state,  de  Montlaur  used  mica  as  a  support  for  platinum,  Zeitsch.  f .  angew.  Chem. 
(1914),  61,  No.  7. 

A  catalyzer  capable  of  bringing  about  reaction  between  air  and  ammonia  to  form 
nitric  oxide  has  been  proposed  by  Schick  (U.  S.  Patent  971,149,  Sept.  27,  1910) 
and  is  based  on  the  use  of  platinum  coated  on  a  suitable  carrier  such  as  quartzite, 
porcelain  and  the  like.  The  spongy  form  of  platinum  is  not  useful  for  the  pur- 
pose, owing  to  undesirable  side  reactions  taking  place  in  the  center  of  the  spongy 
mass.  Accordingly  a  very  thin  surface  layer  of  platinum  is  deposited  on  the  carrier, 
and  to  get  a  coating  of  sufficient  thickness  the  carrier  is  coated  with  a  glaze  such  as 
a  mixture  of  felspar  and  an  alkali  that  will  soften  easily  when  heated.  The  platinum 
material  is  then  baked  on  the  carrier  in  the  presence  of  this  glaze  which  brings  about 
the  formation  of  a  uniformly  thin  layer  of  the  metal.  A  temperature  of  1400°  C. 
is  used. 

In  discussing  the  properties  of  platinum  as  a  contact  material  for  igniting  com- 
bustible gas,  Perl  (U.  S.  Patent  615,363,  Dec.  6,  1898)  states  that  after  the  dis- 
covery that  finely-divided  platinum  did  not  fulfil  the  requirements,  the  endeavor 
was  made  to  increase  the  effect  of  the  finely-divided  platinum  by  mingling  the  same 
with  different  porous  bodies,  according  to  the  suggestion  of  Liebig  (Pogg.  Ann., 
Vol.  17  (1829),  107).  Dobereiner  (Journ.  Praktischer  Chemie,  1839,  Vol.  17,  158) 
went  further  and  prepared  finely-divided  platinum  within  the  pores  of  natural  or 
artificial  meerschaum  or  clay.  Perl  regards  a  method  of  this  character  to  bring 
about  the  formation  of  chloride  of  magnesium  or  other  earths,  because  by  reduction 
of  the  platinum  salts  which  are  in  the  pores  of  the  employed  material  a  part  of  the 
latter  is  always  transformed  by  the  action  of  the  acids  freed  from  the  platinum 
salts  (chiefly  hydrochloric  acid)  into  compounds  which  are  injurious  on  account  of 
their  hygroscopic  properties,  and  which  act  as  fluxes,  causing  the  igniting  material 
to  become  denser  and  more  impenetrable  for  the  gas  after  a  short  time.  To  meet 
these  objections  Perl  proceeds  as  follows: 

Porous  combustible  material  is  thoroughly  mingled  with  a  solid  or  dissolved 
platinum  salt.  The  mixture  is  dried  at  a  moderate  temperature,  and  the  platinum 
*  U.  S.  Patent  1,077,442,  Nov.  4,  1913., 


252  THE  HYDROGENATION  OF  OILS 

is  reduced  in  the  pores  of  the  incombustible  material  by  bringing  the  mixture  to  a 
high  degree  of  heat  in  a  covered  crucible  until  the  hydrochloric  acid  or  the  vapors 
of  any  other  acid  have  disappeared.  The  same  result  is  also  brought  about  by 
heating  the  mixture  in  a  reducing  gas  flame.  The  residual  salts  are  now  extracted 
with  diluted  hydrochloric  acid  and  subsequently  with  water  until  all  trace  of  any 
soluble  salts  removed. 

Efrem  (British  Patent  14,339,  1899;  J.  S.  C.  I.,  1900,  726)  and  Chem.  Fab.  vorm. 
Goldenberg  (British  Patent  618,  1900;  J.  S.  C.  I.,  1901,  250)  employ  clay  and  simi- 
lar supporting  material  for  platinum  in  preparing  catalytic  material.  (See  also 
British  Patents  6448,  1905;  J.  S.  C.  I.,  1906,  432  and  10,729,  1901;  J.  S.  C.  I.,  1902, 
548.) 

C.  E.  Munroe  (U.  S.  Patent  724,317,  March  31,  1903)  produces  a  form  of  plat- 
inum contact  material  active  in  oxidation  processes  by  causing  the  formation  upon 
perforated  sheets  or  disks  of  asbestos  and  upon  sheets  or  disks  of  perforated  metal 
or  woven  wire  of  a  coating  of  finely-divided  platinum.  For  instance,  a  perforated 
sheet  of  asbestos  is  immersed  in  an  alcoholic  solution  of  ammonium  chloride  and 
then  in  an  alcoholic  solution  of  platinic  chloride,  or,  if  preferred,  the  sheet  may  be 
first  immersed  in  the  platinic  chloride  and  subsequently  in  the  ammonium  chloride, 
forming  upon  the  surface  of  the  asbestos  a  crystalline  precipitate  of  ammonium- 
platinic  chloride.  When  the  precipitate  has  been  formed,  the  sheet  of  asbestos  is 
heated.  The  heat  acts  first  to  drive  off  the  alcohol  and  then  decomposes  the  double 
platinum  salt,  leaving  the  metal  in  a  very  finely-divided  state. 

Paal  and  Amberger  *  describe  the  production  of  preparations  of  a 
greasy  consistency  containing  inorganic  metal  colloids  of  the  platinum 
group,  consisting  in  incorporating  solutions  of  the  divalent  salts  of  the 
metals  of  the  platinum  group  with  bodies  maintaining  colloids  in 
the  colloidal  state  (protecting  colloids)  especially  with  wool  fat  or  the 
alcohols  obtainable  therefrom  by  saponification,  and  adding  a  carbon- 
ate of  an  alkali  to  form  the  colloidal  lower  hydroxides  of  the  metals 
employed.  They  note  that  preparations  containing  combinations  of 
the  divalent  salts  of  the  metals  of  the  platinum  group  in  a  colloidal 
condition  can  be  obtained,  if,  instead  of  the  alkali  carbonates  used 
above,  the  alkali  salts  of  certain  weak  organic  acids  are  selected,  for 
instance,  the  salts  of  the  higher,  saturated,  or  unsaturated,  fatty 
acids  (soaps).  In  this  way  there  are  produced  in  the  presence  of 
solutions  of  the  metal  salts,  for  instance,  of  divalent  palladium,  or 
platinum,  triturated  with  wool  fat,  products  which  contain  the  corre- 
sponding palladium,  or  platinum,  salts  dissolved  in  colloidal  form  in 
the  wool  fat. 

If,  according  to  Paal  and  Amberger,  wool  fat  be  impregnated  with  a  concentrated 
aqueous  solution  of  palladious  chloride  (PdCl2)  and  the  mass  be  then  triturated  with 
the  equivalent  quantity  of  potassium  oleate  in  concentrated  aqueous  solution,  the 
salts  mutually  decompose  with  formation  of  potassium  chloride  and  palladious 
oleate  which  remains  dissolved  in  colloidal  form  in  the  wool  fat.  As  the  palladious 
chloride  is  difficultly  soluble  in  pure  water  but  readily  in  hydrochloric  acid  it  is  dis- 

*  U.  S.  Patent  1,077,891,  Nov.  4,  1913. 


THE  RARE  METALS  AS  CATALYZERS  253 

solved  in  the  latter  and  the  acid  is  neutralized  before  triturating  the  liquid  with  wool 
fat  by  means  of  an  amount  of  sodium  carbonate  equivalent  to  the  hydrochloric 
acid  used.  The  neutral  PdCl2  then  remains  dissolved  in  the  liquid. 

In  order  to  obtain  a  preparation  containing  about  25  per  cent  colloidal  palladious 
oleate  0.85  part  of  palladious  chloride  PdCl2  =  0.5  part  of  palladium  are  dis- 
solved with  the  application  of  heat  in  0.45  part  of  fuming  hydrochloric  acid  (38  per 
cent  HC1)  and  2  parts  of  water,  and  the  hydrochloric  acid  is  neutralized  by  the  addi- 
tion of  0.3  part  of  anhydrous  soda  either  solid  or  dissolved  in  0.7  part  of  water. 
The  solution  of  PdCl2  thus  obtained  is  then  triturated  intimately  in  small  portions 
with  9.5  parts  of  wool  fat  softened  at  a  gentle  heat.  Into  the  body  thus  obtained 
are  then  stirred,  also  in  small  portions,  3.5  parts  of  potassium  oleate  dissolved  in 
15  parts  of  water.  The  formation  of  the  palladium  oleate-  is  detected  by  the  fact 
that  the  greasy  mass  colored  red-brown  by  the  palladious  chloride  becomes,  on 
being  triturated  with  the  potassium  oleate,  first  yellow-brown,  then  gray-brown  and, 
after  being  allowed  to  stand  some  considerable  time,  black-brown.  To  purify  the 
product  it  may  be  either  treated  repeatedly  with  hot  water  at  from  50°  to  60°  C., 
and  the  mass  exposed  in  vacuo  at  from  40°  to  50°  C.,  for  the  purpose  of  removing 
the  water;  or  the  original  product  may  be  dissolved  in  from  5  to  6  times  its  vol- 
ume of  petroleum  ether  of  low  boiling  point,  the  greater  part  of  the  by-products 
remaining  undissolved  and  the  red-brown  liquid  organosol  being  dried  with  calcium 
chloride  or  dehydrated  sodium  sulfate.  In  this  case  a  further  part  of  the  by-products 
separates  along  with  the  water.  The  petroleum  ether  is  then  distilled  off  from  the 
liquid  freed  from  the  drying  agent.  The  colloidal  palladium  oleate  can  be  enriched 
in  the  "ointment"  body  by  solution  in  petroleum  ether  and  precipitation  with 
alcohol.  A  product  is  thus  obtained  containing  about  70  per  cent  of  colloidal 
palladium  oleate,  which  like  the  25  per  cent  preparation,  is  absorbed  as  organosol  by 
all  organic  substances  dissolving  wool  fat.  Instead  of  a  palladious  salt,  a  platinous 
or  other  salt  of  the  platinum  group  can  be  used,  for  instance,  the  salt  of  divalent 
platinum  resulting  from  the  reduction  of  the  platinochloride-hydrochloric  acid  with 
sulfur  dioxide.  Wool  fat  impregnated  with  platinous  salt,  when  acted  on  by  an 
aqueous  solution  of  potassium  oleate,  forms  a  colloidal  platinous  oleate  (CisHssC^Pt. 
A  mixture  of  the  wool  fat  alcohols  obtained  from  wool  fat  by  saponification  can  be 
used  in  the  same  manner  as  wool  fat.  The  wool  fat  alcohols  are  in  their  properties 
very  similar  to  the  wool  fat  itself  and  the  mixture  of  alcohols  obtained  therefrom  by 
saponification  presents  a  still  greater  affinity  for  water  than  wool  fat.  The  wool 
fat  alcohols  have  a  more  solid  consistency  than  the  wool  fat.* 

Meyer  f  reports  an  experiment  on  the  hydrogenation  of  olive  oil 
with  a  colloidal  palladium  hydroxide  solution  containing  0.2  gram 

*  Amberger  (Kolloid-Zeit.  (1913),  13,  310)  has  prepared  organosols  of  palladium, 
platinum,  palladious  hydroxide,  palladium  oleate  and  platinous  hydroxide.  In  the 
preparation  of  the  metallic  organosols,  hydrazine  hydrate  was  used  as  a  reducing 
agent.  The  palladium  organosols  (8  :  9  to  16  per  cent  Pd)  had  pronounced  catalytic 
activity;  small  quantities  dissolved  in  fatty  oils  were  capable  of  transferring  hydro- 
gen to  the  unsaturated  glycerides  of  the  oil,  with  the  formation  of  so-called  hardened 
oils.  The  platinum  organosols  contained  8.14  to  18.4  per  cent  Pt.  The  hydroxide 
organosols  were  prepared  by  the  interaction  of  the  corresponding  chlorides  and  sodium 
carbonate  and  the  palladium  oleate  organosols  from  the  chloride  and  potassium 
oleate  in  presence  of  wool  fat.  (J.  S.  C.  I.  (1914),  41.) 

f  Dissertation,  Karlsruhe,  1912. 


254  THE  HYDROGENATION  OF  OILS 

palladium  and  0.34  gram  gum  arable  in  100  cc.  Two  volumes  of 
olive  oil  to  one  volume  of  the  colloidal  solution  were  heated  and  agita- 
ted in  an  autoclave  at  a  temperature  of  70°  to  80°  C.  under  a  hydrogen 
pressure  of  6  atmospheres.  Hydrogen  was  added  to  replace  that 
absorbed.  After  one-half  hour  no  further  absorption  of  hydrogen 
could  be  noted,  but  the  agitation  was  continued  for  2  hours.  The  fat 
was  then  separated  from  the  colloidal  solution  and  boiled  with  water. 
A  solid  fatty  product  was  obtained. 

For  the  purpose  of  combining  hydrogen  with  nitrogen  to  make 
ammonia  the  Badische  Anilin  &  Soda  Fabrik  *  recommend  cerium  and 
a  "promoter  "  as  a  catalytic  agent. 

With  some  exceptions,  compounds  of  the  alkali  metals  and  the  alkaline  earth 
metals  are  said  to  act  as  promoters  of  the  catalytic  power.  Also  oxides  of  the  rare 
earth  metals,  tantalum  and  niobium,  as  well  as  silica,  may  be  employed  as  promoters. 
As  a  general  rule  those  metals  or  compounds  of  the  metals  which  yield  oxides  and 
salts  which  are  non-reducible  by  hydrogen  are  suitable  for  use  as  promoters.  On 
the  other  hand,  the  metalloids,  such  for  instance  as  sulfur,  selenium,  tellurium, 
arsenic,  phosphorus,  and  also  the  easily  fusible  and  easily  reducible  metals,  such  for 
instance  as  lead,  tin  and  zinc,  generally  act  as  contact  poisons,  whether  the  element 
be  added  or  be  present  as  such  or  in  the  form  of  a  compound. 

The  following  example  is  given.  Take  metallic  cerium  which  has  been  prepared 
electrolytically  and  is  in  the  condition  of  small  grains,  and  mix  it  with  about  two 
per  cent  of  its  weight  of  powdered  potassium  nitrate,  and  then  place  the  mixture 
in  the  contact  tube.  On  passing  a  mixture  of  hydrogen  and  nitrogen  through  the 
tube,  while  heating,  a  catalytic  agent  is  obtained  which  is  said  to  give  about  three 
times  the  yield  that  the  untreated  cerium  affords. 

On  account  of  the  high  price  of  osmium  and  ruthenium  or  their  compounds  they 
are  used  by  the  Badische  Co.f  for  catalytic  purposes  on  special  carriers,  in  order  to 
secure  the  greatest  possible  surface  action.  This  is  effected  by  solutions  of  their 
compounds  such  as  alkali  osmate  and  alkali  ruthenate.  The  resulting  contact 
masses  can  be  employed  either  directly  or  after  previous  special  treatment,  such 
as  heating,  action  of  alkalies,  acids,  or  reducing  agents,  etc.  Asbestos,  oxide  of 
magnesium  or  aluminum,  pumice  stone,  meerschaum,  clay,  cement,  kieselguhr, 
metals,  coal,  etc.,  find  application  as  carriers.  For  example,  granulated  meer- 
schaum is  saturated  with  a  solution  of  potassium  osmate  in  dilute  potash  lye, 
and  the  water  evaporated  in  vacuo,  so  that  2  to  5  per  cent  of  osmate  remains 
upon  the  carrier. 

In  order  to  prevent  the  aggregation  of  a  colloidal  compound  such  as  palladium 
hydrate  and  the  like,  it  has  been  suggested  |  to  use  a  solid  fat  in  which  the 
colloidal  particles  are  fixed  so  that  the  organosol  is  rendered  stable.  The  use 
of  a  solid  fat  of  low  iodine  number  such  as  is  prepared  by  hydrogenation  and 
preferably  one  which  has  been  completely  saturated  with  hydrogen  enables  such 
metallic  organosol,  especially  metal  catalyzers,  to  be  preserved  over  an  indefinite 
period. 

*U.  S.  Patent  1,068,968,  July  29,  1913. 

t  German  Patent  No.  292,242,  December  22,  1912. 

J  Kalle  &  Co.,  German  Patent  No.  284,319,  March  1,  1914.  See  also  German  Patents 
268,311  and  289,620  Chem.  Abs.,  1916,  2618. 


THE  RARE  METALS  AS  CATALYZERS  255 

Colloidal  palladium  used  by  Albright  *  in  determining  the  hydro- 
gen number  of  essential  oils  was  a  commerical  product,  f  and  the 
following  is  the  manner  of  its  preparation. f 

A  solution  of  a  palladium  salt  is  added  to  a  solution  of  an  alkali  salt  of  an 
acid  of  high  molecular  weight,  in  this  case  the  sodium  salt  of  protalbinic  acid 
(an  egg  albumin  decomposition  product).  An  excess  of  alkali  dissolves  the  pre- 
cipitate formed  and  the  solution  is  said  to  contain  the  palladium  in  the  form  of 
a  hydrosol  of  its  hydroxide.  This  solution  is  purified  by  dialysis  and  the  hy- 
droxide reduced  with  hydrazine  hydrate.  On  further  dialysis  and  evaporation  to 
dryness  there  is  obtained  a  water-soluble  product  consisting  of  colloidal  palla- 
dium and  sodium  protalbinate  in  the  form  of  black  shining  lamella?,  which 
contains  about  60  per  cent  palladium.  The  sodium  protablinate  present  in  the 
mixture  acts,  when  the  material  is  in  solution,  as  a  "protective  colloid. "§ 

As  is  well  known,  colloids  in  general  are  precipitated,  "  flocked  out,"  by  ions 

I 

(e.g.,  As2S3  by  HC1),  due  to  a  transfer  of  electrical  charges,  but  in  the  presence 
of  a  protective  colloid  relatively  large  amounts  of  electrolytes  are  necessary  to 
bring  this  about. 

Hydrogenation  involving  the  use  of  colloidal  palladium  differs  from  some  other 
processes  of  catalytic  reduction  in  that  the  reaction  has  not  been  observed  to 
proceed  in  the  absence  of  water  nor  if  the  proportion  of  water  in  the  reaction 
mixture  be  too  small.  For  instance,  in  the  case  of  cottonseed  oil,  a  portion  of 
this  material  showed  no  absorption  of  hydrogen  on  being  shaken  with  a  small 
quantity  of  powdered  colloidal  palladium.  The  same  result  was  obtained  whether 
the  oil  was  suspended  in  95  per  cent  alcohol  or  dissolved  in  acetone.  On  adding 
15  to  20  per  cent  of  water  to  the  acetone  solution,  however,  reduction  took  place 
at  a  fairly  rapid  rate,  a  this  more  convenient  form  of  colloidal  palladium  be 
not  available,  a  substitute  may  be  prepared  as  needed  in  the  following  way:|| 
0.05  g.  palladous  chloride  is  placed  in  a  shaking  flask  (see  Fig.  50a,  p.  306),  followed 
by  50  cc.  of  50  per  cent  alcohol  and  1  or  2  cc.  of  a  1  per  cent  aqueous  solution 
of  gum  arabic  (the  weight  of  gum  used  being  about  one-fourth  the  weight  of  the 
PdCl2).  On  shaking  this  mixture  in  an  atmosphere  of  hydrogen,  the  chloride  is 
reduced  with  formation  of  a  black  solution  of  colloidal  palladium,  which  is  ren- 
dered stable,  i.e.,  "  reversible,"  by  the  small  quantity  of  the  reversible  colloid 
present,  gum  arabic.  While  this  solution  may  be  substituted  for  that  of  the 
technically  prepared  substance,  it  is  actually  more  expensive,  as  experiments 
show  that  0.02  g.  colloidal  palladium  costing  $0.048  is  at  least  as  active  as  0.05  g. 
PdCl2,  costing  $0.075.  Paal's  colloidal  palladium  and  palladous  chloride  contain 
approximately  equal  percentages  of  the  metal. 

Certain  substances  are  regarded  as  poisonous  with  respect  to  colloidal  palla- 
dium, for  example,  formaldehyde  contained  in  impure  methyl  alcohol  is  said  to 
be  harmful,  and  allyl  isothiocyanate  entirely  inactivates  it,  so  that  mustard  oil, 
for  example,  cannot  be  treated. 

*J.  Am.  Chem.  Soc.,  1914,  2188. 

t  Prepared  by  Kalle  &  Co.,  Biebrich  am/R.  Price  about  $2.40  per  gram.  See  Paal 
and  Hartman,  Ber.,  43,  248-9,  1910. 

t  Paal  and  Amberger,  Ber.,  37,  124,  1904;   Chem.  Zentr.,  1904,  I,  572. 

§  Paal  and  Amberger,  loc.  cit.,  see  also  Skita  and  Franck,  Ber.,  44,  2862,  1911;  Chem. 
Zentr.,  1911,  II;  173. 

II  Skita  and  Franck,  loc.  cit. 


256  THE  HYDROGENATION  OF  OILS 

A  catalyzer  suitable  for  the  hydrogenation  and  dehydrogenation 
of  oils  or  other  organic  compounds,  is  prepared  according  to  the 
Badische  Company  *  by  treatment  of  an  artificial  zeolite  such  as 
sodium  aluminum  silicate  with  an  acid  solution  of  palladium  chloride,  f 

Fahrion  J  refers  to  the  disadvantages  of  using  so  sensitive  a  cata- 
lyzer as  palladium,  especially  in  view  of  its  high  price  (1  kilo  palla- 
dium costs  6000  M.).  According  to  Connstein  the  loss  in  palladium 
amounts  to  5  to  7  per  cent  of  the  catalyzer  employed,  equivalent 
to  1.10  to  1.20  M.  per  100  kilos  fat.  Bergius  is  reported  by  Fahrion 
as  stating  that  the  loss  is  about  1  g.  of  palladium  per  barrel  of  fat 
hydrogenated. 

At  the  Vereinigte  Chem.  Works  at  Charlottenburg,  hydrogenation 
is  effected  at  100°  C.,  under  a  pressure  of  two  to  three  atmospheres 
by  means  of  0-00002  part  of  palladium  chloride  in  the  presence  of 
an  alkali.  § 

The  rate  of  hydrogenation  is  retarded  in  many  cases  by  the 
presence  of  acids  and  Skita  1 1  has  obtained  certain  colloidal  forms 
of  the  metals  of  the  platinum  group  which  are  considered  more  suit- 
able for  the  purpose  than  acid-liberating  types. 

A  catalyzing  device  proposed  by  Sabatier  and  Mailhe  H  consists  of  a  network 
of  wires,  blades,  rods,  or  tubes  of  catalytic  materials  adapted  to  be  heated  to  the 
necessary  temperatures  by  the  passage  of  an  electric  current.  Metals  of  the 
platinum  or  nickel  series,  or  their  alloys,  or  tantalum  are  suitable  catalytic 
materials,  or  any  metal  coated  with  a  catalytic  metal  may  be  used  as  the  cata- 
lyzing material.  Or  the  electrically  heated  metal  network  may  be  embedded 
in  finely-powdered  metal,  or  in  metal  oxide,  carbonate,  or  other  catalytic  salt, 
suitable  oxides  being  those  of  thorium,  zirconium,  uranium  and  titanium.** 

A  catalyzer  prepared  by  de  Montlaur  for  the  oxidation  of  ammonia,  consists 
of  a  lustrous  and  adherent  deposit  of  metallic  platinum  on  such  inert  material 
as  mica,  glass  or  porcelain.  It  is  obtained  by  coating  the  supporting  sur- 
face with  a  solution  of  a  platinum  tetrachloride  in  an  essential  oil,  preferably 
blue  chamomile  oil,  and  effecting  reduction  at  a  red  heat,  or  by  the  decom- 
position at  a  bright  red  heat  of  sulphur  compounds  of  platinum. ft 

Neumann  proposes  a  support  for  contact  material  platinized  only  at  the  sur- 
face, tt  Porous  supporting  material  is  first  subjected  to  a  treatment  by  which 
an  insoluble  precipitate  is  formed  in  its  pores.  For  example,  it  may  be  treated 
first  with  potassium  silicate  and  then  with  hydrofluosilicic  acid,  or  first  with 

*  British  Patent  No.  8,462,  April  3,  1914. 

f  Cf .  Mittasch,  Schneider  and  Morawitz,  following. 

J  Die  Hartung  der  Fette,  Braunschweig,  1915,  p.. 34. 

§  Colletas,  Les  Matures  Grasses,  1914,  7,  4151. 

||  Seifen.  Ztg.,  1914, 1213. 

1  British  Patent  No.  2,011,  February  8,  1915;    Chem.  Abs.,  1916,  2032. 

**  See  French  Patent  No.  475,367,  February  14,  1914;    J.  S.  C.  I.,  1916,  32. 

ft  French  Patent  No.  445,857,  September  15,  1911. 

Jt  German  Patent  No.  218,725,  May  2,  1908;  J.  S.  C.  I.,  1910,  487. 


.       THE  RARE  METALS  AS  CATALYZERS  257 

barium  chloride  and  then  with  sulphuric  acid.  It  is  then  washed,  dried  and 
platinized  by  heating  and  spraying  with  a  platinum  solution  containing  a  reduc- 
ing agent,  after  which,  it  is  washed  with  water  or  with  acids  in  which  the  pre- 
cipitate is  insoluble.  By  this  method  less  platinum  is  used  than  by  the  process 
described  in  German  Patent  No.  188,503.* 

A  contact  substance  for  catalytic  reactions  described  by  Niedenfuhrf  consists 
of  a  hollow  perforated  metal  support  coated  with  platinum  electrolytically  or 
otherwise. 

Commenting  on  British  Patent  No.  18,642  to  the  Vereingte  Chemische  Werke, 
Fokin  t  states  that  in  1906  he  §  published  a  communication  on  the  reduction  power 
of  platinum  hydroxide  and,  in  fact,  had  made  application  for  patent  in  Russia  in 
April,  1909.  In  1910  ||  he  published  a  further  communication  in  which  the  theory 
of  the  process  and  the  function  of  the  three  factors,  namely;  the  hydrogen  atom, 
the  hydroxyl  group,  and  the  double  bond  were  discussed.  Fokin  observed  that 
complex  compounds  of  platinum  were  formed  which  are  organosols.  These 
possess  a  surface  of  "  unlimited "  area,  which  accelerate  the  reaction  in  Nthe 
highest  degree.  Later  in  a  publication  on  the  preparation  of  isomers  of  oleic 
acid  the  procedure  was  more  fully  detailed  by  Fokin  and  methods  of  determining 
the  hydrogen  number  were  described,  in  which  platinum  oxide  was  used  as  the 
catalytic  agent,  f 

Galactose,  resulting  from  protracted  boiling  of  aqueous  glue  solutions,  is 
advanced  by  Classen  *  *  as  a  protective  colloid  for  finely -divided  metals,  a  salt  of 
the  metal  being  reduced  in  the  presence  of  this  agent. 

The  protective  action  of  a  number  of  colloids  has  been  determined  by  Groh  ft 
by  measurements  of  the  extent  to  which  they  retard  the  catalytic  decomposition 
of  hydrogen  peroxide  by  colloidal  platinum.  The  following  values  show  the 
times  required  by  colloidal  platinum  to  effect  50  per  cent  decomposition  of  the 
peroxide  without  and  in  the  presence  of  protective  colloids.  Without  a  protective 
colloid  twenty  minutes,  0.1  per  cent  gelatin  two  hundred  and  sixty-five  mintues, 
0.1  per  cent  gum  arabic  eighty-six  minutes,  0.1  per  cent  dextrin  sixty-six  minutes, 
0.01  per  cent  gelatin  one  hundred  and  fifty  minutes,  0.01  per  cent  gum  arabic 
thirty-nine  minutes,  0.01  per  cent  dextrin  twenty-eight  minutes,  0.001  per  cent 
gelatin  one  hundred  and  three  minutes,  0.001  per  cent  gum  arabic  twenty-one 
minutes,  0.001  per  cent  dextrin  twenty-three  minutes,  0.0001  per  cent  gelatin 
seventy-one  minutes.  J| 

Zelinsky  §§  has  shown  that  catalytic  dehydrogenation  by  palladium  or  plat- 
inum appears  to  be  characteristic  of  hexamethylene  hydrocarbons  and  may  be 
used  for  the  separation  of  pentamethylene  and  hexamethylene  hydrocarbons  and 
to  the  investigation  of  petroleum  distillates.  A  mixture  of  methylcyclopentane 
and  cyclohexane  was  subjected  three  times  in  succession  to  the  action  of  platinum 

*  J.  S.  C.  I.,  1908,  502. 

t  German  Patent  No.  225,705,  July  31,  1908. 
J  Chem.  Ztg.,  1913,  61. 

§  Journ.  Russ.  Phys.  Chem.  Gesell.,  1906,  419  and  Zeit.  Electrochem,  12,  749. 
||  Journal  Russ.  Phys.  Chem.  Gesell.,  1910,  1074. 

f  Zeit.  Analyt.  Chemie,  48,  337,  and  Journ.  Russ.  Phys.  Chem.  Gesell.,  1908,  700. 
**  Zeitsch.  angew.  Chem.  Referat.,  1915,  58,  German  Patent  No.  281,305,  March'30, 
1913. 

>t  Z.  physik.  Chem.,  88,  414. 
JJChem.  Abs.,  1915,  7. 
'§§  Ber.,  1912,  3678;  J.  S.  C.  I..  1913,  76. 


258  THE  HYDROGENATION  OF  OILS 

black  at  300°  C.;  the  quantity  of  hydrogen  evolved  was  93.4  per  cent  of  the 
theoretical  quantity  calculated  for  the  converson  of  cyclohexane  into  benzene. 
The  product  was  treated  with  sulphuric  acid  (2  vols.  of  acid  of  sp.  gr.  1.84 
mixed  with  1  volume  of  fuming  acid  containing  7  per  cent  of  anhydride),  which 
sulphonated  the  benzene;  the  residual  unattacked  hydrocarbon,  after  distillation 
over  sodium  had  the  properties  of  the  original  pure  methylcyclopentane.  A 
fraction  (boiling-point  102°  to  104°  C.,  sp.  gr.  0.7647  at  18°  C.),  from  Baku 
petroleum,  after  purification  by  treatment  with  sulphuric  acid  of  the  strength 
mentioned  above,  when  treated  in  a  similar  manner  yielded  toluene  and  a  hydro- 
carbon (boiling-point  101°  to  102.5°  C.  sp.  gr.  0.7488  at  20°/4°  C.)  which  was 
probably  a  derivative  of  cyclopentane  or  cyclobutane.  A  petroleum  fraction 
(boiling-point  100°  to  100.5°  C.)  obtained  by  repeated  treatment  of  so-called 
"  naphtha-heptanaphthene  "  with  a  mixture  of  nitric  and  sulphuric  acids,  gave 
similar  results. 

Normann  and  Schick  hold  that,  contrary  to  the  views  of  Leh- 
mann,  osmium  metal  and  not  the  dioxide,  is  responsible  for  the 
catalytic  action  noted  in  fat  hardening.* 

Colloidal  hydroxides  of  osmium  and  ruthenium  and  the  colloidal  metals 
themselves  may  be  prepared  according  to  Kalle  und  Co.  A.  G.f  by  means  of  a 
protective  colloid.  The  tetroxide  of  osmium  or  of  ruthenium  is  mixed  with  the 
protective  colloid,  such  as  sodium  protalbinate  or  lysalbinate,  and  with  alcohol, 
and  the  mixture  evaporated  carefully  to  dryness.  The  solid  colloidal  hydroxide 
thus  obtained  may  be  reduced  to  the  colloidal  metal  by  means  of  hydrogen  at  a 
low  temperature.  The  advantage  of  this  modification  is  found  in  avoiding  the 
admixture  of  salts  and  alkalies  and  in  the  fact  that  dialysis  is  not  necessary. 
The  preparation  in  detail  is  as  follows: 

One  part  sodium  protalbinate  is  dissolved  in  200  to  300  parts  water  and  then 
1.34  parts  osmium  tetroxide  in  about  60  volumes  cold  alcohol  is  added.  The 
mixture  is  then  either  evaporated  to  dryness  in  vacuo,  or  else  gently  heated  on 
the  water-bath  to  remove  most  of  the  solvent  and  finally  dried  in  vacuo.  The 
osmium  tetroxide  is  reduced  by  the  alcohol  to  the  tetrahydroxide  Os(OH)4. 
If  evaporation  is  effected  in  pleno,  ammonia  must  be  added  from  time  to  time  in 
order  to  prevent  reoxidation  of  the  hydroxide  to  the  volatile  oxide.  If  the 
process  is  applied  to  ruthenium  tetroxide,  the  alcohol  must  be  added  to  the 
solution  of  the  protalbinate  or  lysalbinate  of  sodium,  and  the  tetroxide,  dissolved 
in  water  is  allowed  to  flow  gradually  in  the  solution  with  stirring.  Ruthenium 
chloride,  RujCle,  or  the  potassium  salt  of  the  acid  may  be  used  as  the  initial 
material,  which  is  first  converted  by  treatment  in  a  current  of  chlorine,  in  the 
presence  of  water  with  heating,  into  the  tetroxide.  If  the  osmium  or  ruthenium 
hydroxides  are  to  be  converted  into  the  corresponding  colloidal  metals,  the  solid 
products  are  carefully  powdered  and  treated  in  a  tube  freed  from  air  by  carbon 
dioxide  with  hydrogen  at  30°  to  40°,  obtaining  thereby  colloidal  Os  or  Ru.  If 
the  colloidal  tetrahydroxides  are  to  be  obtained  in  dilute  aqueous  solution,  a 
smaller  amount  of  stabilizer  will  be  sufficient.  J 

*Seifen.  Ztg.,  1914,  1111;   Arch.  Pharm.,  1914. 

t  German  Patent  No.  280,365,  July  30,  1913.  Addition  to  German  Patent  No.  248,525; 
J.  S.  C.  I.,  1915,  492  and  1912,  952. 

JChem.  Abs.,  1915,  1378;   Zeitsch.  angew.  Chem.,  Referat,  1915,  22. 


THE   RARE   METALS  AS  CATALYZERS  259 

Osmium  and  ruthenium  compounds  are  used  as  catalyzers  in  the  synthesis 
of  ammonia.  Asbestos,  meerschaum,  or  similar  material  is  soaked  in  a  solution 
of  alkali  osmate,  or  alkali  ruthenate,  and  dried.  The  contact  mass  thus  obtained 
can  be  employed  for  catalytic  purposes  either  directly,  or  after  being  heated,  or 
acted  upon  with  acid  or  reducing  agents.*  Osmium  as  an  oxidizing  catalyst  is 
described  by  Hofmann.f  Ruthenium  is  favored  by  Mittasch  as  a  hydrogenating 
catalyzer,  J 

By  supporting  platinum  on  charcoal,  a  catalyzer  is  obtained, 
according  to  Mannich,§  which  is  free  from  the  disadvantages  of 
colloidal  platinum  and  is  more  efficient  than  the  metal  on  an  indif- 
ferent carrier.  Purified  animal  charcoal  is  recommended.  A  plat- 
inum black  charcoal  catalyzer  has  been  found  to  absorb  great  quan- 
tities of  hydrogen.  The  results  obtained  on  castor  and  peanut  oils 
show  distinctly  advantageous  results.  Palladium  supported  on  small 
pieces  of  coke  is  used  as  a  catalyzer  by  Verona-Rinati.|| 

Platinum  and  carbon,  especially  charcoal,  in  admixture,  have  been 
found  by  Ellis  to  afford  a  desirable  catalytic  agent.  If  In  preparing  the 
catalyzer,  care  is  taken  to  exclude  oxygen.  The  cerium  group  of 
metals  as  hydrogen  carriers  is  considered  by  Ellis,**  who  recommends 
cerium  incorporated  with  charcoal. 

By  the  addition  of  animal  charcoal  Mannich  and  Thiele  ft  find  the 
absorption  capacity  of  palladium  for  hydrogen  is  greatly  increased, 
and  the  mixture  absorbs  much  more  gas  than  the  total  quantity 
absorbed  by  the  separate  constituents.  A  catalyst  which  rapidly 
effects  the  complete  hydrogenation  of  fats  is  prepared  by  shaking 
powdered,  ignited  animal  charcoal  with  palladium  chloride  (prefer- 
ably 2  per  cent)  solution  and  hydrogen  until  no  more  gas  is  absorbed. 
The  powder  is  then  washed  and  dried  and  can  be  kept  unaltered. 
It  can  be  used  in  conjunction  with  any  solvent  and,  after  hydro- 
genation, is  completely  separated  by  simple  filtration,  without  leaving 
any  trace  of  metal  in  the  fat.  In  these  respects  it  is  superior  to 
colloidal  palladium  preparations. 

An  oil  such  as  peanut  oil  can  be  hydrogenated  by  means  of  «i>  of  its  weight 
of  animal  charcoal  containing  0.2  per  cent  palladium  (ratio  of  metal  to  oil  = 
1  :  30,000)  into  a  tallow-like  mass,  with  M.P.  51°  C.  and  iodine  value  45.5. 

*  Badische  Co.,  British  Patent  No.  12,977,  June  4,  1913. 

t  British  Patent  No.  20,593,  September  11,  1913;   Chem.  Abs.,  1915,  697. 

JjU.  S.  Patent  No.  1,173,532,  February  29,  1916. 

§  Seifen.  Ztg.,  1914,  1174. 

||  Annali  Chim.  Appl.,  1914,  99. 
H[U.  S.  Patent  No.  1,174,245,  Mar.  7,  1916. 
I**  U.  S.  Patent  No.  1,167,280,  Jan.  4,  1916. 
[ft  Ber.  Deutschen  Pharm.  Ges.,  1916,  26,  36-48;  J.  S.  C.  I.:  1916,  548. 


260  THE   HYDROGENATION  OF  OILS 

Even  by  the  use  of  1  part  of  palladium   (distributed  over  animal  charcoal)  to 
150,000  parts  of  peanut  oil  the  hardening  can  be  effected  in  one  operation. 

A  catalyzer  used  in  the  production  of  propylene  by  the  union  of 
acetylene  and  methane  and  containing  two  catalytic  metals  is  pre- 
pared by  Heinemann  *  in  the  following  manner: 

One  of  the  contact  metals,  for  example,  copper,  is  deposited  in  a  porous  body, 
for  example,  pumice  stone,  either  electrolytically,  or  by  the  reduction  of  a  copper 
salt.  The  pumice  stone,  provided  with  a  coating  of  copper,  or  having  its  pores 
partly  filled  with  copper,  is  then  dipped  in  a  solution  of  a  salt  of  a  contact  metal 
of  the  platinum  class,  for  instance,  chloride  of  platinum,  and  is  dried.  The  salt 
is  then  reduced.  In  this  way  there  is  obtained  a  contact  body  consisting  of 
two  metals  which  are  stated  to  exert  a  mutual  balancing  effect  on  one  another, 
the  more  active  property  of  the  platinum  group  metal  being  mitigated  by  the 
less  active  property  of  the  other  metal  associated  therewith,  and  allowing  the 
desired  reaction  to  take  place  at  a  moderate  temperature. 

Bbeseken  and  Hofstedef  carried  out  experiments  on  the  absorption 
of  hydrogen  by  cinnamic  acid  and  its  esters,  using  a  palladium  solution 
prepared  according  to  the  method  of  Skita  and  Meyer  and  found  con- 
siderable irregularity  in  the  velocity  of  the  reaction  under  what  were 
thought  to  be  comparable  conditions.  The  presence  of  small  amounts  of 
oxygen  in  the  hydrogen  was  found  to  exert  a  marked  activation  of  the 
catalyzer.  It  is  concluded  that  even  in  this  apparently  simple  catalytic 
reduction,  viz.,  an  irreversible  reaction  with  elementary  catalyzer, 
the  phenomena  are  far  more  complicated  than  could  be  expected. 

An  interesting  form  of  catalyzer  investigated  by  Mittasch, 
Schneider  and  Morawitz  J  contains  the  elements  of  a  metal  of  the 
platinum  group  and  an  aluminate  silicate,  and  can  be  obtained  by 
taking  an  aluminate  silicate  containing  water,  such  as  a  natural  or 
artificial  zeolite,  and  replacing  a  part  or  the  whole  of  its  content  of 
alkali  metal  or  alkaline  earth  metal,  by  the  platinum  metal. 

The  product  obtained  can  be  subjected  to  further  treatment.  For  instance, 
it  may  be  heated  and  reduced,  and  this  reduction  is  desirable  if  the  catalytic 
agent  is  to  be  employed  for  the  hydrogenation  of  organic  compounds.  After 
such  reduction,  the  catalytic  agent  contains  a  platinum  metal  in  a  metallic  form 
and  also  the  elements  of  an  aluminate  silicate. 

The  introduction  of  the  platinum  metal  into  the  silicate  can  be  effected  by 
digesting  the  alkali  metal  aluminate  silicate  with  a  solution  of  a  platinum  metal 
salt.  Or,  the  zeolite  as  obtained  (or  after  being  gently  heated,  so  that  some  of 
the  water  is  driven  off)  may  be  soaked  in  a  solution  of  a  platinum  metal  salt, 

*  U.  S.  Patent  No.  1,202,385,  October  22,  1916. 

t  Proc.  Akad.  Wetensch.,  Amsterdam,  1918,  20,  424;  Chem.  Abs.,  1918,  1144;  J.  S.  C.  I., 
1918,  136A. 

J  U.  S.  Patent  No.  1,215,396,  February  13,  1917.  See  also  British  Patent  1,358, 
Jan.  27,  1915. 


THE  RARE  METALS  AS  CATALYZERS  261 

so  that  the  platinum  metal  salt  enters  the  zeolite,  and  some  replacement  of  the 
alkali  metal  or  alkaline  earth  metal  by  a  platinum  metal  takes  place,  although  the 
alkali  remains  in  the  mass. 

Example:  Digest  100  parts  of  the  artificial  zeolite,  sodium  alumina te  silicate 
such  as  the  ordinary  commercial  granular  sodium  permutite  found  on  the  market) 
with  a  weak  hydrochloric  acid  solution  containing  one-tenth  of  a  part,  to  half  a 
part,  of  palladium  subchloride,  either  at  ordinary  temperature,  or  while  warming, 
until  the  solution  is  decolorized.  If  the  catalytic  agent  is  to  be  used  for  hydro- 
genation  purposes,  wash  the  mass  well  and  dry  it  and  reduce  with  hydrogen  at  from 
150°  to  200°  C.,  or  with  formaldehyde  at  a  lower  temperature.  The  catalytic 
agent  which  is  obtained  can  be  used  (either  directly,  or  after  pulverization)  for 
the  hydrogenation  or  dehydrogenation  of  organic  compounds,  and,  when  liquids 
are  treated,  these  can  with  advantage  be  allowed  to  trickle  over  the  catalytic 
agent.  Instead  of  sodium  permutite,  other  aluminate  silicates  containing  an 
easily  replaceable  base,  or  more  than  one  easily  replaceable  base,  can  be  em- 
ployed, for  instance,  natural  zeolites  can  be  used,  such  as  analcime,  natrolite, 
chabasite.  In  a  similar  manner,  other  platinum  metal  zeolites  can  be  prepared, 
for  instance,  those  of  platinum  itself  and  of  rhodium,  iridium,  ruthenium  and 
osmium.  A  platinum  zeolite  can  be  obtained  by  heating  an  artificial  zeolite 
until  more  or  less  of  the  water  has  been  driven  off,  and  then  soaking  it  in  a 
solution  of  platinum  hydrochloride,  drying  and  heating,  whereupon,  any  soluble 
salts,  such  as  sodium  chloride  can  be  removed  by  washing  or  digesting.  An 
osmium  zeolite  can  be  prepared  by  soaking  a  zeolite  in  a  solution  of  potassium 
osmate,  and  heating.  The  artificial  or  natural  zeolite  can  first  be  converted 
into  ammonium  zeolite,  and  this  either  directly  or  after  heating  can  be  con- 
verted into  osmium  zeolite,  by  treatment  with  potassium  osmate.* 

Amberger  f  states  that  practically  all  previous  preparations  of 
colloidal  osmium  have  resulted  in  a  colloidal  oxide  or  hydroxide. 
Amberger  has  prepared  organosols  of  platinum  and  palladium  in 
wool  fat  and  now  applies  the  same  principle  to  the  preparation  of 
colloidal  osmium. 

Two  parts  of  osmium  tetraoxide  are  dissolved  in  7  parts  dilute  caustic  soda 
and  alcohol  added  till  sodium  osmate  is  formed.  This  is  gradually  stirred  into 
13  parts  of  warm  wool  fat,  intimately  mixed,  then  hydrazine  hydrate  is  added 
slowly;  the  emulsion  swells  and  takes  on  a  metallic  grey  color  and  on  standing 
twenty-four  hours  becomes  black.  Another  warming  and  the  addition  of  more 
hydrazine  hydrate  are  necessary  for  complete  reduction.  To  remove  by-products 
the  mass  may  be  dissolved  in  petroleum  ether,  washed,  dried  and  the  ether  dis- 
tilled off.  There  results  a  brown-black  salve,  easily  soluble  in  organic  liquids 
which  dissolve  wool  fat,  giving  transparent,  brownish  black  liquids.  For  analysis 
this  salve  is  dissolved  in  petroleum  ether,  precipitated  by  more  than  an  equal 
volume  of  alcohol  and  osmium  determined  in  the  dry  precipitate  by  the  method 

*  Artificial  zeolites  are  put  on  the  market  under  the  names  of  permutite,  and  are  de- 
scribed in  British  Patent  No.  23,706/12  and  also  in  the  article  "  On  Artificial  Zeolites  " 
by  Siedler,  on  page  262  of  the  report  of  Section  2  of  the  Seventh  International  Congress 
of  Applied  Chemistry  held  in  London  in  1909. 

t  Kolloid-Z.,  17,  47-51,  1915;  Chem.  Abs.,  1915,  3159. 


262  THE  HYDROGENATION  OF  OILS 

of  Knotte.*  The  osmium  content  is  about  7.9  per  cent.  This  contains  oxides  of 
osmium  as  well  as  metallic  osmium.  In  order  to  reduce  the  colloidal  oxides 
the  original  emulsion,  after  reduction  with  hydrazine  hydrate,  is  dissolved  in 
petroleum  ether  and  precipitated  by  alcohol;  nearly  all  the  osmium  precipitates 
in  combination  with  a  large  proportion  of  the  wool  fat.  This  coagulum  is 
washed  free  from  alkali,  dried,  powdered  and  then  reduced  with  dry  hydrogen 
first  in  the  cold  then  at  30°  to  50°.  This  gives  a  stable  organosol,  easily  soluble 
in  liquids  which  dissolve  wool  fat.  The  osmium  content  is  20.9  per  cent.  If 
instead  of  reducing  the  sodium  osmate  wool  fat  emulsion  with  hydrazine  hydrate, 
sulphuric  acid  is  added,  an  organosol  of  osmium  dioxide  is  formed,  one  prepara- 
tion of  which  gave  0.53  per  cent  osmium  dioxide.  By  dissolving  in  petroleum 
ether  and  precipitating  with  alcohol,  then  washing,  the  concentration  may  be 
raised  to  an  osmium  dioxide  content  of  24.5  per  cent. 

Silicic  acid  is  used  by  Schwerin,f  to  form  stable  colloidal  solutions  of  metals' 
for  example,  a  solution  of  silicic  acid  containing  about  2.5  per  cent  of  the  acid 
is  mixed  with  a  diluted  solution  of  a  gold  or  silver  salt  and  the  metal  is  re- 
duced by  a  reducing  agent  suitable  for  separating  it  in  the  colloidal  form.  If, 
for  instance,  hydrazin  hydrate  is  the  reducing  agent  a  completely  clear  brown 
silver  sol,  or  deep  blue  gold  sol,  is  obtained. 

By  the  method  of  SchwarcmanJ  a  precipitated  sesquioxide  is  treated 
with  a  soluble  salt  of  a  platinum  group  metal,  such  as  palladium, 
until  a  certain  amount  of  active  compound  is  deposited;  the  treated 
sesquioxide  is  then  dried  at  a  comparatively  low  temperature,  best 
after  thorough  washing;  the  hydrated  sesquioxide  being  advan- 
tageously formed  under  conditions  permitting  adsorption  or  absorp- 
tion of  colloid  organic  matter,  such  as  keratin  dissolved  in  caustic 
alkali. 

The  sesquioxide  may  be  ferric  hydrate,  chromium  hydrate  or  aluminum 
hydrate,  the  latter  giving  best  results.  Other  hydrated  non-basic  or  slightly- 
acid  oxides,  such  as  hydrated  tin  oxide,  titanic  acid,  tungstic  acid,  etc.,  may  be 
used  but  have  no  particular  advantage  over  the  sesquioxides.  Hydrated  oxides 
of  the  type  of  cobalt  oxide,  nickel  oxide  and  zinc  oxide,  for  general  hydrogenation 
work  are  stated  to  be  far  inferior  to  the  sesquioxides.  Palladium  is  the  best 
metal  of  the  platinum  group  to  use  for  the  purpose  of  hydrogenating,  although 
platinum  compounds  may  be  used  for  this  purpose,  and  for  oxidizing  are  even 
better.  Osmium,  ruthenium,  and  rhodium  also  may  be  used. 

The  hydrated  sesquioxides  although  not  active  as  hydrogenating  agents 
per  se,  according  to  Schwarcman  appear  to  heighten  the  activity  of  palladium 
in  some  degree  as  "  cocatalysts."  This  is  said  to  be  particularly  true  with 
palladium  hydroxide  distributed  through  hydrated  alumina.  Anhydrous  alumina, 
as  a  carrier,  he  states  affects  the  activity  of  palladium  but  little  if  at  all.  The 
hydrated  oxides  are  all  readily  soluble  in  dilute  acids,  which  is  convenient  in 
regenerating  the  catalyst. 

*  Z.  angew.  Chem.,  15,  393,  1902. 

tU.  S.  Patent  No.  1,119,647,  December  1,  1914. 

JU.  S.  Patent  No.  1,111,502,  September  22,  1914. 


THE  RARE  METALS  AS  CATALYZERS  263 

According  to  a  formula  by  Schwarcman,  342  parts  of  aluminum  sulphate, 
Alj  (804)3,  are  dissolved  in  3400  parts  of  water  and  the  temperature  is  adjusted 
to  about  170°  F.  A  solution  of  240  parts  of  commercial  caustic  soda  or  the 
equivalent  amount  of  carbonate,  in  1000  parts  of  water  at  about  the  same  tem- 
perature, is  then  added.  The  addition  of  soda  results  in  the  precipitation  of 
hydrated  alumina.  This  precipitate  is  washed  until  all  the  soluble  salts  have 
been  removed.  The  hydrate  so  obtained  is  next  treated  to  incorporate  palladium. 
For  this  purpose  0.312  part  of  palladium  chloride  are  dissolved  in  100  parts  of 
water  and  the  hydrated  alumina  treated  with  this  solution.  The  mixture  then 
is  brought  to  a  boil,  filtered  and  the  solid  material  washed.  This  treatment 
leaves  the  alumina  charged  with  merely  the  quantity  of  palladium  it  will  absorb. 
The  material  after  washing  is  dried  at  a  moderate  temperature.  A  high  tem- 
perature is  apt  to  cause  dehydration  of  the  palladium  oxide,  and  of  the  alumina 
as  well,  to  an  undesirable  extent.  A  drying  temperature  of  about  170°  is  best. 
Using  the  amounts  of  materials  indicated,  there  will  be  obtained  about  156  parts 
of  a  fine-grained  brown  powder  containing  approximately  0.2  per  cent  palladium. 
Generally  most  of  this  palladium  exists  in  the  catalyst  in  the  form  of  a  hydrate. 

A  more  active  catalyst  in  a  somewhat  different  physical  form  is  obtained  by 
using  a  little  keratin  or  other  organic  colloid  dissolved  in  the  caustic  soda  used 
for  forming  the  hydrated  alumina.  Wool  is  very  well  suited.  The  same  reagents 
in  the  same  proportions  may  be  used  together  in  the  manner  indicated  above 
with  the  exception,  that  about  5  parts  of  wool,  are  previously  dissolved  in  the 
caustic  soda  solution.  The  final  material  obtained  is  more  fluffy  and  bulky 
than  where  the  wool  is  omitted.  This  fluffy  bulky  catalyst  is  kept  in  suspen- 
sion in  the  oil  with  particular  readiness. 

Schwarcman  states  that  since  palladium  oxide  does  not  form  soaps  with  fatty 
acids,  it  may  be  employed  in  hydrogenating  free  oily  and  fatty  acids  and  that  as 
alumina  is  insoluble  in  fatty  acids,  the  palladium  carried  by  this  sesquioxide 
makes  a  particularly  good  catalyst  for  this  purpose. 

Sulzberger  *  considers  that  the  most  efficient  way  of  intimately 
distributing  a  catalyzer  is  by  dissolving  the  initial  catalytic  material 
in  the  body,  which  is  to  be  treated,  and  then,  should  not  the  form, 
?n  which  the  material  was  dissolved  in  the  body,  be  per  se  catalyt- 
ically  active,  transforming  it  by  chemical  reaction  or  otherwise  into 
a  product  of  catalytical  efficiency. 

As  an  example,  he  cites  the  hardening  of  cottonseed  oil  with  a  catalytic  agent 
belonging  to  the  platinum  group:  palladium.  Sulzberger  notes  that  a  palladium 
product  of  the  desired  quality  can  be  obtained  by  treating  a  palladium  salt,  as 
for  instance,  "  palladium-ammonium  chloride  "  with  sodium  oleate,  which  result- 
ing compound  is  soluble  in  cottonseed  oil  and  can  be  used  a:  a  catalyzer  of 
highest  efficiency,  as,  being  so  finely-divided  in  the  oil,  even  very  small  quanti- 
ties will  give  good  results.  The  solution  of  this  product  in  the  oil  darkens  when 
heated,  in  consequence  of  its  palladium  content  and  such  solution  hardens  to  a 
product  of  jelly-like  consistency  at  certain  temperatures  and  when  containing 
certain  amounts  of  the  palladium  body.  Cottonseed  oil,  when  containing  this 
body  is  readily  hardened  when  treated  with  hydrogen. 

*  U.  S.  Patent  No.  1,171,902,  February  15,  1910. 


264  THE  HYDROGENATION  OF  OILS 

i 

In  cases  where  the  product,  which  is  to  act  as  a  catalyzer,  cannot  be  mada 
use  of  in  a  form  soluble  in  the  body  which  is  to  be  treated  catalytically,  the 
very  fine  distribution  of  the  catalytic  agent  may  be  accomplished  by  dissolving 
it  in  a  solvent,  which  mixes  with  the  body  to  be  treated,  with  or  without  pre- 
cipitation. For  example,  the  above  palladium  compound  being  soluble  in  ether, 
could  be  added  to  the  cottonseed  oil  in  such  solvent. 

Killing  *  employs  a  composition  of  thorium  oxide  and  a  metal  of  the  platinum 
group  in  a  state  of  very  fine  division  as  a  catalyst  in  a  gas  igniting  device. 
In  producing  this  material  nitrate  of  thorium  and  chloride  of  platinum,  are  mixed, 
afterward  ashing  or  burning  out  the  mixture,  producing  a  fixed  sponge  of  thorium 
oxide  and  platinum  black.  The  proportions  which  Killing  has  found  best  suited 
to  the  end  in  view  are  1  part  of  thorium  nitrate  to  2  to  2^  parts  of  platinum 
black.  Iridium  and  other  metals  of  the  platinum  group  may  be  substituted  for 
platinum  or  mixed  therewith  without  destroying  the  efficiency  of  the  compound. 
Other  rare  earths  may  be  substituted  for  the  thorium,  as,  for  instance,  cerium, 
and  zirconium. 

The  effect  of  the  hydroxides  or  oxides  of  iron,  copper,  mercury  and  zinc  on  the 
catalytic  activity  of  palladium  hydrosol  has  been  studied  by  Paal  and  Hartmann.f 
Ferric  hydroxide  has  no  action  while  copper  hydroxide  lowers  the  activity.  Zinc 
hydroxide  at  first  depresses  the  activity  but  after  a  time  the  catalyst  becomes  more 
than  normally  active.  Yellow  mercuric  oxide  permanently  impairs  the  activity 
of  the  hydrosol. 

Users  of  platinum  in  catalytic  reductions  have  begun  to  recognize  that  it  some- 
times matters  whether  the  catalyst  is  entirely  free  from  occluded  oxygen  at  the 
outset  or  has  been  freely  exposed  to  the  air.  For  example,  Hesst  has  shown  that  the 
rigid  exclusion  of  oxygen  is  necessary  in  order  to  insure  success  in  the  reduction  of 
pyrrole  and  some  of  its  derivatives.  Willstatter  and  Jaquet§  describes  cases  of  the 
opposite  kind,  in  which  the  catalyst  must  be  activated  by  exposing  it  to  oxygen  at 
intervals.  The  most  interesting  example  is  phthalic  anhydride.  If  this  is  dis- 
solved in  glacial  acetic  acid  and  treated  with  hydrogen  in  the  presence  of  platinum- 
black,  only  a  small  volume  of  gas  is  absorbed,  unless  the  apparatus  is  opened  as 
occasion  requires  and  the  catalyst  is  agitated  in  contact  with  the  air.  Then  the 
reduction  proceeds  smoothly  to  hexahydrophthalic  acid.  It  appears,  therefore,  that 
platinum  and  oxygenated  platinum  must  be  regarded  as  distinct  catalysts.  (See 
page  260.) 

*  U.  S.  Patent  No.  614,557,  Nov.  22,  1898. 

t  Ber.  1918,  31,  894  and  711;  J.  S.  C.  I.,  1918,  560A,  579A. 

J  Ber.  1913,  46,  3120,  4104. 

§  Ber.  1918,  51,  767;  J.  S.  C.  I.,  1918,  560A;  J.  Chem.  Soc.,  1918,  i.,  391. 


CHAPTER    XI 

THE    OCCLUSION   OF  HYDROGEN   AND   THE   MECHANISM 
OF  HYDROGEN  ADDITION 

As  an  acquaintance  with  the  subject  of  hydrogen  addition  and 
reduction  by  hydrogen  of  various  bodies  may  lead  to  a  broader  knowl- 
edge of  catalytic  reactions  in  the  hydrogenation  of  oils,  the  following 
notes  by  various  observers  are  included. 

Sie verts  and  Krumhaar*  did  not  find  hydrogen  to  be  absorbed  by 
the  metals  cadmium,  thallium,  zinc,  lead,  bismuth,  tin,  antimony, 
silver  and  gold.  The  solubility  in  copper,  nickel,  iron  and  palladium 
is  shown  in  the  graphic  curve  diagram.  (Fig.  50.) 

The  curves  show  that  the  solubility  increased  regularly  with  the  temperature  up 
to  the  melting  point  and  then  suddenly  increased,  the  solubility  in  the  liquid  metal 
then  increasing  regularly  in  the  same  manner.  With  palladium,  however,  the 
solubility  was  independent  of  the  temperature  up  to  the  melting  point  and  then 
diminished  to  one-half,  and  in  the  liquid  metal  was  again  independent  of  the  temper- 
ature. On  cooling,  copper  retained  20  per  cent  and  nickel  8  per  cent  of  the  hydrogen 
absorbed,  and  in  the  case  of  iron,  the  evolution  of  gas  was  so  violent  on  solidification 
that  the  tube  was  blown  to  pieces,  leaving  a  spongy  regulus.  In  experiments  with 
alloys  it  was  found  that  the  addition  of  gold  lowered  the  solubility  of  oxygen  in 
silver.  The  copper  alloys  and  hydrogen  formed  three  groups:  (a)  those  in  which 
the  solubility  was  not  influenced,  such  as  silver;  (6)  those  in  which  the  solubility 
was  lowered,  such  as  gold,  tin,  aluminium;  (c)  those  in  which  the  solubility  was 
higher  than  that  accounted  for  by  the  copper  content,  such  as  nickel  and  platinum. 
The  solubility  in  copper  alloys  was  proportional  to  the  square  root  of  the  pressure, 
and  the  view  that  occlusion  was  due  to  adsorption  is  untenable,  and  although  Sieverts 
and  Krumhaar  hold  the  view  that  adsorption  did  not  exist  at  high  temperatures, 
they  do  not  express  any  opinion  about  low  temperature  conditions,  and  they  put 
forward  the  view  that  gases  and  metals  form  solid  and  liquid  alloys,  the  solubility 

of  which  does  not  follow  Henry's  law,  but  is  expressed  by  the  formula        . 

m 

Exhaustive  data  are  given  by  Sieverts  (Z.  physik.  Chem.  (1911),  591)  of  the 
solubilities  of  hydrogen  in  the  three  metals,  copper,  iron  and  nickel,  at  pressures  up 
to  1.5  atmospheres,  and  temperatures  from  400°  to  1600°  C.  It  is  shown  in  the  case 
of  nickel  that  the  amount  of  gas  absorbed  by  the  metal  under  given  conditions  of 
temperature  and  pressure  is  independent  of  the  amount  of  metallic  surface.  The 
hydrogen-containing  metals  are  therefore  true  solutions.  At  constant  temperature 
the  solubility  both  in  solid  and  liquid  metals  is  proportional  to  the  square  root  of 

the  gas  pressure,  the  quotient  — (where  m  is  the  mass  of  gas  absorbed  by  100  grams 

*  Berichte  (1910),  43,  893. 
265 


266 


THE  HYDROGENATION  OF  OILS 


6.6 


6.0 


Pd+Hi 


The  ordlnate  denotes  milligrams 
The  ordinate  denotes  C5  njilligrams 
The  ordlnate  denotes  m 


f a  dissolved  in  100  gr.  metal 
dissolved  in    1  gr.    ^.g 
dissolved  in  o'.5  gr;  Cu 


0.5 


o.o 


1000  1100          1200  1300          1400  1500          1600       1700  C 

FIG.  50. 


THE  OCCLUSION  OF  HYDROGEN  267 

of  metal)  being  remarkably  constant  for  values  of  p  above  10  mm.  At  constant 
pressure  the  solubility  increases  with  temperature,  and  shows  a  sudden  increase  at 
the  melting  points  of  all  three  metals.  The  transition  from  ft  to  y  iron  is  also  marked 
by  a  rapid  increase  in  solubility  between  850°  and  900°  C.  This  discontinuity  though 
very  marked  is  not  so  sudden  as  that  at  the  melting  point.  The  transition  from  a 
to  /3  iron  is  not  accompanied  by  any  change  in  solubility.  In  the  liquid  metals  the 
solubility  continues  to  increase  with  rise  of  temperature,  probably  more  rapidly  than 
in  the  solid  state.  On  solidifying  in  an  atmosphere  of  hydrogen  all  three  metals 
"spit."  Copper  gives  off  about  twice  its  volume  of  hydrogen  (at  1084°  C.  and 
760  mm.)  iron  about  7  times  its  volume  (at  1510°  C.  and  760  mm.)  and  nickel  about 
12  times  its  volume  (at  1450°  C.  and  760  mm.).  The  regulus  contains  cavities  in 
which  hydrogen  may  be  retained.  It  is  only,  however,  after  very  rapid  cooling  that 
any  considerable  quantity  of  the  absorbed  hydrogen  can  be  retained  at  ordinary 
temperatures. 

With  regard  to  the  occlusion  of  hydrogen  by  various  metals,  the 
following  table  is  instructive.*  The  numbers  indicate  the  volumes  of 
hydrogen  under  normal  conditions  absorbed  by  one  volume  of  the 
metal. 

Silver  wire 0.21 

Silver  powder 0.91-0.95 

Sheet  aluminum 1 . 1-2 . 7 

Reduced  cobalt 59-153 

Copper  wire 0.3 

Reduced  copper 0 . 6-4 . 8 

Iron  wire 0 . 46 

Cast  iron 0.57-0.8 

Reduced  iron 9 .4-19 .2 

Magnesium 1.4 

Reduced  nickel 17-18 

Gold  leaf 0.48 

Precipitated  gold 37^6 

Molten  lead * 0.11-0.15 

Zinc Traces 

From  a  study  of  the  action  of  nickel  and  hydrogen  on  various  hydro- 
carbons at  different  temperatures,  the  following  conclusions  are  drawn 
by  Padoa  and  Fabrisf:  (1)  In  the  dehydrogenation  of  monocyclic 
and  polycyclic  hydrogenized  hydrocarbons,  gaseous  hydrocarbons  are 
formed  to  some  extent.  .  If  a  hydrocarbon  yields  several  hydro- 
genation  products,  the  most  highly  hydrogenized  one  is  most  readily 
decomposed  in  this  manner.  Of  the  hydrocarbons  examined,  tetra- 
and  di-hydrophenanthrene  yielded  no  hydrocarbon  decomposition 

*  Abegg  and  Auerbach,  Hdb.  d.  Anorganischen  Chemie  Vol.  II,  part  I,  55. 
t  J.  S.  C.  I.  (1908),  1083. 


268  THE  HYDROGENATION  OF  OILS 

products  even  under  increased  pressure,  and  tetrahydronaphthalene 
did  not  under  atmospheric  pressure. 

(2)  The  decomposing  action  of  nickel  is  influenced  by  pressure. 

For  instance,  at  atmospheric  pressure,  tetrahydronaphthalene  is 
simply  dehydrogenized  with  liberation  of  hydrogen,  whereas  under  a 
pressure  of  3  atmospheres,  gaseous  hydrocarbons  are  formed.  (3)  The 
several  hydrogenation  products  of  a  hydrocarbon  can  each  be  obtained 
from  the  most  highly  hydrogenized  product  by  the  action  of  nickel  at 
a  definite  temperature,  but  it  is  not  possible  to  effect  a  gradual  pro- 
gressive splitting  off  of  hydrogen.  In  almost  all  cases  dehydrogenation 
begins  at  a  higher  temperature  than  hydrogenation.  Under  atmos- 
pheric pressure  hydrogenation  and  dehydrogenation  are  distinct  proc- 
esses; in  most  cases  nickel  can  effect  either  reaction,  but  on  certain 
compounds,  the  nickel  acts  only  in  one  way.  Under  increased  pressure, 
the  two  limits  of  temperature,  viz.,  the  highest  at  which  hydrogenation 
is  possible  and  the  lowest  at  which  dehydrogenation  takes  place,  are 
closer  together,  and  under  certain  conditions,  the  two  processes  may 
proceed  simultaneously  until  equilibrium  is  attained. 

Relative  to  its  behavior  to  hydrogen,  Holt,  Edgar  and  Firth  *  state 
that  palladium  may  exist  either  in  an  active  or  a  passive  state,  the 
former  rapidly  taking  up  hydrogen,  the  latter  being  practically  inert. 
Heating  to  a  temperature  of  400  degrees  in  hydrogen  and  cooling 
renders  the  palladium  very  active.  New  palladium  may  be  made 
active  by  the  repeated  oxidation  and  reduction  of  the  surface.  The 
activity  diminishes  gradually  on  standing,  but  may  be  restored  on 
heating. 

When  spongy  palladium  was  exposed  to  hydrogen  at  temperatures  from  —  50°  C. 
upwards,  Gutbier  (Ber.  (1913),  1453)  found  that  the  amount  of  occluded  gas  steadily 
decreased  from  —50°  C.  (917  volumes  to  1  of  palladium)  to  a  minimum  at  20°  C. 
(661  :  1)  then  slowly  rose  to  105°  C.  (754  :  1).  The  hydrogenized  palladium  was 
pyrophoric. 

It  is  suggested  that  the  activity  is  due  to  the  presence  of  a  metastable  modifica- 
tion of  the  palladium  which  gradually  reverts  to  a  more  stable  variety  at  ordinary 
temperature.  Measurements  have  been  made  of  the  rate  of  sorption  (this  term 
includes  both  adsorption  and  absorption)  of  hydrogen  by  palladium  free  from  hydro- 
gen, and  palladium  containing  varying  amounts  of  previously-sorbed  hydrogen. 
No  marked  difference  was  observed  between  the  action  of  moist  and  dry  hydrogen. 
With  palladium  containing  little  or  no  hydrogen  the  rate  of  sorption  first  increases 
rapidly  and  then  slowly  diminishes.  On  the  other  hand,  if  the  palladium  has  al- 
ready sorbed  considerable  quantities  of  hydrogen  the  initial  increase  is  not  observed. 
It  would  appear  that  when  active  palladium  is  exposed  to  an  atmosphere  of  hydrogen 
there  is  first  a  rapid  condensation  (adsorption)  of  the  gas  at  the  surface,  probably 
in  the  form  of  complex  molecules,  forming  a  layer  of  high  vapor  pressure.  This  is 

*  Z.  physik.  Chem.,  82,  513. 


THE  OCCLUSION  OF  HYDROGEN  269 

followed  by  a  slow  diffusion  (absorption)  into  the  interior  of  the  metal.  This  would 
explain  the  rapid  rise  in  pressure  followed  by  slow  increase  observed  when  palladium 
partially  saturated  with  hydrogen  is  exposed  to  a  vacuum.  The  sorption  is  accom- 
panied by  evolution  of  heat.  Measurements  were  also  made  of  the  rate  of  diffusion 
of  hydrogen  through  a  palladium  tube.  The  rate  is  found  to  increase  with  rise  in 
temperature,  but  it  is  also  influenced  by  the  state  of  the  metal.  This  accounts  for 
the  fact  that  the  same  diffusion  velocity  is  not  always  found  at  the  same  temperature. 
It  is  very  doubtful  that  the  hydrogen  sorbed  by  the  palladium  is  at  the  same  con- 
centration throughout  the  metal,  even  after  long  standing. 

The  rate  of  absorption  of  hydrogen  by  limonene  in  the  presence  of  platinum  black 
has  been  studied  by  Vavon  (Comp.  rend.  (1914),  158,  410),  and  two  stages  or  phases 
of  the  reaction  were  noted.  The  velocity  curves  for  the  absorption  of  hydrogen 
have  a  gradient  which  varies  considerably  with  the  quantity  of  catalyst  present. 
Apparently  the  metal  can  become  fatigued  so  that  while  it  is  active  enough  to  bring 
about  the  easier  stages  of  hydrogen  addition,  it  is  not  powerful  enough  to  effect  the 
more  difficult  stages  of  saturation.  This  is  more  marked  after  the  catalyst  has  been 
heated  to  a  temperature  of  300°  C.  or  higher,  when  the  activity  can  be  varied  and 
suited  to  bring  about  hydrogenation  in  a  selective  and  regular  manner.  When 
heated  above  500°  C.  platinum  black  is  transformed  into  an  inactive  modification. 

The  work  of  Andrew  and  Holt  (Proc.  Roy.  Soc.  (1913),  A.  89,  170),  which  leads  to 
the  conclusion  that  palladium  is  dimorphic,  is  discussed  by  Halla  (Z.  physik.  Chem. 
(1914),  86,  496),  who  shows  that  palladium  black  prepared  by  Graham's  method  is 
not  inactive.  He  also  shows  that  occlusion  by  active  palladium  is  not  hindered  at 
ordinary  temperatures  by  contact  with  the  inactive  metal. 

Mixtures  of  hydrogen  and  oxygen  combine  with  explosion  on  contact  with 
platinum  or  carbon  which  has  been  heated  to  a  temperature  sufficient  to  cause 
the  emission  of  electrically-charged  particles  from  the  surfaces  of  platinum  or  carbon. 
If  platinum  is  exposed  to  Roentgen  rays  which  cause  the  emission  of  charged  par- 
ticles an  explosion  may  be  brought  about  without  heating  the  platinum.  (J.  R. 
Thompson,  Chem.  Ztg.,  Rep.  (1914),  15.) 

Investigations  directed  towards  an  explanation  of  the  precise  nature 
of  hydrogen  transfer  by  means  of  the  platinum  metals  are  not  lacking. 
Wieland*  assumes  that  palladium  hydride,  or  for  that  matter  any 
metal  hydride,  unites  as  such  with  the  unsaturated  compound  at  the 
double  bond  and  that  the  labile  addition  product  breaks  down,  with 
retention  of  the  hydrogen  and  elimination  of  palladium,  the  latter 
being  then  in  condition  to  take  up  additional  hydrogen  and  again 
form  an  addition  product.  From  a  thermodynamic  standpoint  the 
hydrogenation  process  appears  to  be  a  reversible  reaction.  In  the 
case  of  ethylene  compounds,  and  in  fact,  in  general,  the  reaction  is 
exothermic,  but  is  endothermic  in  the  case  of  the  double  bonding  of 
the  aromatic  series.  Thus  the  metal  addition  product  would  appear 
in  the  reaction  equilibrium  as  follows: 


*  Ber.,  45,  484. 


270  THE  HYDROGENATION  OF  OILS 

In  this  connection  it  may  be  stated  that  Skita  and  associates  have 
isolated  an  addition  product  of  palladium  chloride  with  an  unsaturated 
body  but  work  along  this  line  has  not  been  extensive  and  the  explana- 
tion advanced  that  catalyzers  simply  split  the  hydrogen  molecule  to 
yield  hydrogen  in  an  atomic  or  nascent  condition  is  for  the  present 
perhaps  as  satisfactory  as  any.* 

Troost  and  Hautef euille  f  believed  that  their  experiments  vindicated 
the  formation  of  a  definite  compound  Pd2H,  while  Dewarf  suggested 
the  existence  of  PdsH^.  The  experiments  of  Hoitsema§  indicate  that 
between  20  and  200  degrees  no  definite  compounds  of  palladium  and 
hydrogen  exist. 

Sabatierll  considers  nickel  catalysis  to  be  due  to  the  formation  of 
hydrides.  First  hydrogen  acts  on  the  metal,  quickly  forming  a  com- 
pound in  the  superficial  layers  of  the  latter.  The  hydride  which  re- 
sults becomes  decomposed,  and  in  the  presence  of  bodies  which  are 
capable  of  hydrogen  addition,  union  with  the  hydrogen  takes  place. 
The  metal  is  regenerated  and  the  role  endlessly  repeated. 

The  variations  in  activity  of  nickel  which  have  been  noted  probably 
depend  on  the  formation  of  different  hydrides.  Thus,  for  example, 
well-prepared  nickel  catalyzer  may  form  the  perhydride  NiH2  which 
is  sufficiently  active  to  hydrogenate  benzol.  Nickel  prepared  at  high 
temperatures,  or  if  slightly  poisoned,  may  form  the  lower  hydride 
NiH 

1 1      which  is  not  active  on  benzol  but  which  is  catalytic  for  olefines 
NiH 
and  nitro  compounds. 

Were  this  assumption  correct  it  would  appear  as  a  consequence  that 
nickel  and  the  other  active  metals  (copper,  iron,  cobalt  and  platinum) 
not  only  should  effect  a  union  of  hydrogen,  but  also  that  hydrogen- 
containing  compounds  should  suffer  removal  gf  their  combined  hydro- 

*  Some  experimental  work  of  Paal  (Ber.,  45,  2221)  is  of  interest.  Paal  notes 
that  apparently  only  those  compounds  with  two  C  :  C  groups  in  which  these  groups 
are  separated  by  at  least  one  carbon  atom  can  be  catalytically  reduced  stepwise. 
Thus  PhCH  :  CHCH  :  CHAc  in  alcohol  with  colloidal  palladium  and  two  hydrogen 
equivalents  give  about  50  per  cent  each  of  the  original  ketone  and  of  the  fully  re- 
duced compound  (PhCH2)  Ac.  Similar  results  were  obtained  with  PhCH  :  CHCH  : 
C(CO2H)2,  piperinic  acid  and  piperine.  Phorone,  on  the  other  hand,  yields  almost 
quantitatively  dihydrophorone,  Me2CHCH2COCH  :  CMe2,  b.  176  degrees;  semi- 
earbazone,  needles,  m.  p.  133  to  134  degrees.  (Chem.  Abs.) 

f  Comp.  rend.,  (1874),  78,  686. 

t  Chem.  News,  (1897),  76,  274. 

§  Zeit.  phy.  Chemie  (1895),  1. 

II  Die  Hydrierung  durch  Katalyse,  Leipsic  (1913),  17. 


'OCCLUSION  OF  HYDROGEN 

gen,  the  metals  acting  as  dehydrogenating  catalyzers.  This  actually 
proves  to  be  the  case.  Between  250°  to  300°  C.  finely-divided  copper 
readily  acts  as  a  dehydrogenating  catalyst,  converting  primary  alcohols 
to  aldehydes  and  secondary  alcohols  to  ketones,  in  fact  affording  a 
very  advantageous  method  for  bringing  about  these  transformations. 
Results  obtained  by  hydrogenation  with  nickel.  The  results  obtained 
by  hydrogenation  with  reduced  nickel  are  classed  by  Sabatier  into  4 
groups : 

1.  Simple  reduction  without  the  fixation  of  hydrogen. 

2.  Reduction  effected  simultaneously  with  the  fixation  of  hydrogen. 

3.  Fixation  of  hydrogen  by  addition  to  the  molecules  where  multiple 
bonds  exist. 

4.  Hydrogenation  effected  with  the  decomposition  of  the  molecule. 

The  well-established  impossibility  of  effecting  all  these  changes  with 
any  metal  leads  Sabatier  to  think  that  for  nickel  there  exists  many 
degrees  of  combination  with  hydrogen.  Nickel  obtained  by  the  reduc- 
tion of  the  chloride,  as  well  as  that  reduced  at  a  temperature  above 
400°  C.  is,  without  doubt,  able  to  produce  only  a  primary  hydride, 
analogous  to  that  of  copper  and  capable  of  acting  on  nitro  groups  or 
on  the  double  ethylene  bond.  Only  "  healthy  "  nickel,  such  as  that 
produced  by  the  reduction  at  a  low  temperature  of  the  oxide  obtained 
from  the  nitrate,  is  able  to  form  a  perhydride  capable  of  hydrogenating 
the  aromatic  ring. 

In  the  case  of  nickel  oxide  catalyzers  Erdmann  indicates  that  the 
transference  of  hydrogen  probably  takes  place  in  one  of  two  ways: 
either  an  intermediate  phase  represented  by  the  compounds 


Hi 

HC-Ni 


-  NK  H  -  NK. 

O     and  >  O 

H  -  Ni/ 

or  a  decomposition  of  water  may  take  place  in  accordance  with  the 
reaction : 

Ni2O  +  H2O  =  2  NiO  +  H2 

yielding  hydrogen  in  a  nascent  state  which  is  assumed  to  unite  with 
the  unsaturated  fat  while  the  nickel  oxide  formed  is  reduced  to  the 
suboxide  by  hydrogen  in  the  molecular  condition. 

In  an  experiment  conducted  by  Mayer  and  Altmayer*  nickel, 
reduced  from  the  oxide  by  hydrogen,  was  introduced  into  a  Jena  glass 
vessel  in  an  electric  furnace,  and  after  complete  exhaustion,  known 

*  Berichte  (1908),  41,  3062. 


272  THE  HYDROGENATION  OF  OILS 

quantities  of  hydrogen  were  introduced,  and  the  temperature  kept 
constant  until  absorption  ceased.  The  amount  absorbed,  at  tempera- 
tures of  360°  to  560°  C.,  was  at  each  temperature  proportional  to 
the  pressure  of  the  hydrogen.  At  360°  C.  1  volume  of  nickel  absorbed 
50.5  volumes  of  hydrogen  at  a  pressure  of  300  mm.,  whilst  at  560°  C. 
the  same  absorption  occurred  when  the  pressure  was  raised  to  440  mm. 
Within  the  experimental  limits,  then,  the  system  nickel-hydrogen  is 
bivariant,  the  volume  absorbed  being  dependent  both  on  temperature 
and  on  pressure. 

|  Amorphous  palladium  absorbs  hydrogen  far  more  rapidly  than  the 
crystalline  form,  but  holds  it  only  feebly.  The  amorphous  form  also 
takes  up  hydrogen  and  transmits  it  to  the  crystalline  variety,  so  that 
crystalline  palladium  coated  with  the  amorphous  metal  will  absorb 
hydrogen  much  more  rapidly  than  when  uncoated.* 

Adsorption  is  quite  variously  regarded  by  various  authorities  as 
one  of  the  following:  (1)  True  chemical  combination.  (2)  True 
solid  solution.  (3)  A  modified  solid  solution  in  which  practically 
only  the  outer  layers  become  saturated  owing  to  the  difficulty  of  dif- 
fusion in  solids.  (4)  Condensation  on  the  outside  of  the  surface  of 
the  solid.  According  to  McBain  f  the  first  three  are  contrary  to  the 
requirements  of  thermodynamic  theory,  and  the  fundamental  assump- 
tion of  the  third  is  disproved  by  experiments  involving  the  time 
required  for  adsorption  of  hydrogen.  The  fourth  is  found  insufficient 
to  explain  the  somewhat  complex  time  relationships  studied  here,  which, 
however,  point  strikingly  to  the  conclusion  that  both  true  solid  solu- 
tion (true  diffusion)  and  surface  condensation  occur.  They  are  inde- 
pendent of  each  other  and  their  relative  importance  and  magnitude 
depend  upon  the  conditions  of  the  experiment. 

The  non-committal  name  "sorption"  is  coined  to  designate  the  sum  total  of 
the  phenomena,  while  "absorption"  and  "adsorption"  are  restricted  to  the  dis- 
solved and  superficially-condensed  matter  respectively.  It  is  found  that  the  surface 
condensation  requires  only  a  few  minutes  for  completion,  whereas  absorption  requires, 
in  the  case  of  hydrogen  diffusing  into  carbon  at  the  temperature  of  liquid  air,  a 
dozen  hours  for  practical  completion.  Thus  it  was  possible  to  isolate  the  two  phe- 
nomena and  to  study  them  more  or  less  independently  of  each  other.  For  instance, 
by  suitable  manipulation  a  sample  of  carbon  can  be  prepared  highly  charged  with 
hydrogen  in  a  state  of  solid  solution  but  almost  destitute  of  occluded  hydrogen 
condensed  on  the  surface.  This  is  clearly  attainable  (if  the  hypothesis  be  correct) 
by  suddenly  exposing  to  a  vacuum  carbon  which  has  been  previously  saturated  by 
long  contact  with  hydrogen  at  a  constant  temperature.  Such  carbon,  exposed  to  a 
low  pressure  of  hydrogen  and  cut  off  from  all  external  influences,  took  up  hydrogen 

*  Proc.  Roy.  Soc.,  London  (A),  89,  170-186,  Chem.  Abs.  (1914),  457. 
t  Seventh  Int.  Cong.  Appl.  Chem.,  1909. 


THE  OCCLUSION  OF  HYDROGEN  273 

at  first  (surface  condensation)  although  already  supersaturated  (i.e.,  in  respect  to 
the  solid  solution),  and  then  gave  it  off  again  in  still  greater  quantity  until  final 
equilibrium  was  established.  Thus  the  manometer  first  fell  for  a  few  minutes  and 
then  rose  to  a  higher  point  than  the  initial  value.  In  the  converse  case,  where  the 
interior  was  saturated  by  a  very  short  exposure  to  a  high  pressure  of  gas,  hydrogen 
was  first  given  off,  and  then  taken  up  again  by  diffusion  into  carbon.  Here  the 
manometer  automatically  rose  for  a  few  minutes,  then  steadily  fell  for  many  hours 
to  a  lower  value  than  previously  obtained.  The  pressure  changes  observed  might 
at  first  seem  unimportant,  were  it  not  for  the  one  fact  of  great  significance,  viz., 
that  (taking  the  second  case  just  outlined)  the  higher  pressure  at  five  minutes  was 
even  less  than  corresponded  to  the  gas  condensed  on  the  surface  of  the  carbon,  yet 
after  a  dozen  hours  had  elapsed  a  much  lower  pressure  was  attained,  a  pressure 
which  then  actually  did  correspond  to  the  condensed  gas  in  equilibrium  with  it. 
Thus  a  considerable  body  of  hydrogen  had  been  transferred  from  the  surface  to  the 
interior  of  the  carbon.  An  approximate  calculation  of  the  extent  of  this  transfer 
showed  that  the  true  solubility  of  hydrogen  at  the  temperature  of  liquid  air  and 
under  2  cm.  pressure  was  at  least  4  c.c.  (corr.)  per  gram  of  the  cocoanut  carbon 
employed.  This  absorption  was  roughly  proportional  to  the  square  root  of  the 
pressure  (whereas  the  total  sorption  varies  as  the  cube  root  of  the  pressure).  From 
this  it  appears  that  the  dissolved  hydrogen  is  split  up  into  single  atoms. 

Tomassi  *  considers  that  the  reductions  caused  by  hydrogen  at  the 
moment  of  its  liberation  from  its  compounds  are  wrongly  attributed 
to  its  being  in  an  allotropic  condition,!  such  as  is  usually  connoted  by 
the  term  "  nascent  ";  for,  in  that  case,  he  argues,  the  same  reactions 
ought  always  to  follow  whatever  the  origin  of  the  gas;  but  this  is  not 
borne  out  by  experiment. 

Thus,  silver  chloride,  bromide  or  iodide,  suspended  in  water  acidulated  with 
sulfuric  acid,  can  be  reduced  by  the  hydrogen  liberated  from  water  by  electrolysis, 
but  show  no  signs  of  reduction  when  the  water  is  decomposed  with  sodium  amalgam. 
Or,  if  a  solution  of  potassium  chlorate  be  acidulated  with  sulfuric  acid,  and  zinc 
added,  the  chlorate  is  reduced  to  chloride;  whereas  if  sodium  amalgam  be  added, 
no  reduction  takes  place.  Nor  does  sodium  amalgam  bring  about  the  reduction 
of  chloric  acid  or  of  the  chlorates  of  sodium,  barium,  copper,  lead  or  mercury.  In 
the  case  of  potassium  perchlorate,  none  of  the  usual  reducing  agents  have  any 
effect;  zinc  or  magnesium  with  sulfuric  acid,  or  zinc  with  potash  or  soda,  or  in  a 
boiling  solution  of  copper  sulfate,  all  failing  to  bring  about  reduction,  but,  on  the 
other  hand,  this  is  readily  effected  by  sodium  hydrosulfite  —  a  compound  from 
which  hydrogen  is  not  liberated.  Similarly,  a  solution  of  nickel  sulfate,  to  which 
potash  and  potassium  cyanide  have  been  added,  acquires  a  reddish  tint  on  the  addi- 
tion of  zinc,  while  hydrogen  is  liberated;  but  if  magnesium,  or  a  magnesium-platinum 
couple,  replace  the  zinc,  the  red  color  is  no  longer  produced,  although  hydrogen  is 
still  liberated.  Kern  found  (Bull.  Soc.  Chim.,  26,  338)  that  by  the  action  of  mag- 
nesium on  ferric  chloride,  ferric  hydroxide  was  produced,  and  this  fact  Tomassi  con- 
firms, with  the  addition  that  he  obtains  the  same  result  by  using  sodium  amalgam 

*  Monit.  Scient.,  1898  [51],  182. 

t  It  has  been  suggested  by  Osann  that  active  or  occluded  hydrogen  is  in  an 
allotropic  form  comparable  to  ozone. 


274  THE  HYDROGENATION  OF  OILS 

instead  of  magnesium.  According  to  Stahlschmidt,  nascent  hydrogen  derived  from 
the  decomposition  of  water  by  zinc  dust  reduces  potassium  nitrate  to  nitrite,  reduced 
iodides  and  iodates,  but  does  not  reduce  chlorates;  and  De  Wilde  has  established 
the  fact  that  sodium  amalgam  reduces  potassium  bromate,  but  is  without  action  on 
the  chlorate. 

On  these  and  similar  facts  Tomassi  bases  his  opinion  that  the  reducing  power  of 
nascent  hydrogen  varies  according  to  the  chemical  reaction  by  which  the  hydrogen 
was  produced,  and  he  considers  that  if  the  gas  has  a  greater  affinity  in  the  nascent 
than  in  the  ordinary  condition,  this  is  entirely  due  to  the  hydrogen  at  the  moment 
of  its  liberation  from  a  compound  being  accompanied  by  the  heat  produced  during 
the  liberation.  Hence,  if  nascent  hydrogen  be  represented  by  the  symbol  H  +  a 
(in  which  a  denotes  this  amount  of  heat),  the  value  of  a  would  vary  with  each  chem- 
ical reaction,  and,  as  a  general  rule,  the  reducing  power  of  nascent  hydrogen  would  be 
proportional  to  that  value,  provided  that  the  reaction  between  the  hydrogen  and 
the  substance  to  be  reduced  could  once  be  started.  There  are  certain  cases,  how- 
ever, in  which  the  reduction  is  due,  not  to  the  hydrogen,  but  to  the  metal  which 
served  to  generate  it.  The  reduction  of  potassium  chlorate  by  means  of  sulfuric 
acid  and  zinc,  or  by  electrolysis  of  its  solution  with  a  zinc  anode,  is  an  instance  of 
this.  If  such  a  solution  be  electrolyzed  with  both  electrodes  of  platinum,  oxidation 
occurs  at  the  anode,  with  the  formation  of  perchlorate,  while  no  trace  of  chloride 
is  found  at  the  cathode;  but  if  a  zinc  anode  be  used,  chloride  is  formed  at  the  anode, 
but  not  at  the  cathode.  From  this  Tomassi  concluded  that  the  reduction  in  this 
case  must  be  attributed,  not  to  the  hydrogen,  but  to  the  zinc  uniting  with  the  oxygen 
of  the  chlorate  in  accordance  with  the  equation  KC1O3  +  3  Zn  =  KC1  +  3  ZnO. 

Titoff*  has  studied  the  adsorption  of  hydrogen  and  other  gases  by 
pure  gas-free  cocoanut  charcoal.  The  temperature  varied  from  —  79° 
to  +  151.5°  C.,  and  the  pressures  from  0  to  77  cm.  of  mercury.  The 
results  are  given  in  tables  and  the  relations  illustrated  by  isothermal 
and  isobaric  curves.  Hydrogen  appears  to  obey  Henry's  law  for  a 
considerable  range  of  temperature  (—  80°  to  +  80°  C.).  Titoff  pre- 
fers a  surface  condensation  theory  as  an  explanation  of  the  phenomena, 
and  consequently  he  uses  the  term  adsorption,  rather  than  absorption, 
which  would  seem  to  suggest  ordinary  solution. f 

Firth  observes  that  the  adsorption  of  hydrogen  (surface  condensation) 
by  wood  charcoal  occupies  only  a  few  minutes,  while  the  equilibrium 
due  to  absorption  is  attained  only  after  several  hours,  hence  "sorp- 
tion"  is  of  a  two-fold  character.  Wood  charcoal  contains  crystalline 
as  well  as  amorphous  carbon  and  the  activity  of  the  material  depends 
chiefly  on  the  latter.  J 

*  Z.  physik.  Chem.  (1910),  74,  641;  see  also  Homfray,  J.  S.  C.  I.  1910,  1055. 

t  Rhead  and  Wheeler  (Chem.  Soc.  Proc.  (1913),  29,  51)  observe  that  carbon,  at 
all  temperatures  up  to  900°  C.  and  probably  above  that  temperature,  has  the  power 
of  pertinaciously  retaining  oxygen.  This  oxygen  cannot  be  removed  by  exhaustion 
alone,  but  may  be  expelled  by  increasing  the  temperature  of  the  carbon  during 
exhaustion.  When  quickly  released  in  this  manner,  it  appears,  not  as  oxygen,  but 
as  carbon  dioxide  and  carbon  monoxide. 

J  Z.  physik.  Chem.  (1914),  294;  J.  S.  C.  I.  1914,  130. 


THE  OCCLUSION  OF  HYDROGEN  275 

The  presence  of  kaolin  favors  the  combination  of  hydrogen  and 
oxygen  at  temperatures  from  230  degrees  and  upwards.  Without  the 
kaolin,  combination  does  not  take  place  until  a  temperature  of  350  de- 
grees or  higher  is  reached.  The  activity  of  the  kaolin  depends  greatly 
upon  the  temperature  to  which  it  has  previously  been  heated,  and  the 
extent  to  which  it  has  lost  its  water  of  constitution.  The  lower  the 
water  content,  the  less  pronounced  is  the  activity.* 

It  has  been  stated  by  Marie  f  and  Petersen|  that,  in  the  electrolytic 
reduction  of  unsaturated  acids,  the  nature  of  the  cathode  used  has  no 
appreciable  influence  upon  the  course  and  velocity  of  the  reaction. 
Fokin§  finds,  however,  that  reduction  can  only  be  effected  with  cath- 
odes of  palladium,  platinum,  rhodium,  ruthenium,  iridium,  osmium, 
nickel  cobalt  and  copper,  and  that  the  quantity  and  the  physical 
condition  of  the  metal  has  a  considerable  influence  on  the  course  of  the 
reduction.  It  is  shown  that  the  metals  named  have  the  capacity  of 
occluding  hydrogen,  with  the  formation  of  unstable  hydrides.  It  is 
these  metals,  also,  which  have  been  found  to  act  as  hydrogen-carriers 
in  the  reduction  processes  studied  by  Sabatier  and  Senderens.  Fokin 
is  of  the  opinion  that  all  reduction  processes  taking  place  in  presence 
of  the  metals  mentioned,  viz.,  electrolytic  reduction,  reduction  of 
gaseous  substances  by  reduced  metals  by  the  process  of  Sabatier  and 
Senderens,  reduction  by  galvanic  couples,  and  reduction  by  metal 
hydrides  in  solutions,  are  due  to  a  special  activity  of  the  occluded 
hydrogen,  probably  owing  to  such  hydrogen  being  in  the  monatomic 
condition.  The  activity  of  the  metals  varies  directly  with  their 
capacity  of  occluding  hydrogen;  palladium  is  the  most  efficient,  and 
then  follow,  in  the  order  given,  platinum,  nickel,  cobalt  and  copper. 
Fokin  has  studied  in  this  way  the  reduction  of  the  fatty  acids  from 
linseed  oil,  Japanese  wood  oil,  castor  oil,  cod-liver  oil,  and  other  un- 
saturated acids. 

According  to  Fokin  the  metals  can  be  grouped  into  those  which, 
like  palladium  and  cobalt,  form  definite  hydrides;  and  those  which, 
like  platinum  and  nickel,  have  not  been  proved  to  form  such  definite 
hydrides.  The  latter  class  gives  the  best  results  in  reduction  catal- 
yses.!! By  the  action  of  excess  of  cobalt  hydride  at  270°  C.,  under 
atmospheric  pressure,  oleic  acid  is  reduced  to  stearic  acid  to  the  extent 

*  J.  S.  C.  I.  1914,  254,  and  Comp.  rend.  (1914),  158,  501. 
t  Compt.  rend.,  136,  1331;  J.  S.  C.  I.  1903,  1003. 
j  Z.  Elecktrochem.,  11,  549;  J.  S.  C.  I.  1905,  895. 

§  J.  russ.  phys.  chem.  Ges.  (1906),  38,  419;  Chem.  Centr.  (1906),  2,  758;  J.  S. 
C.  I.  1906,  935. 

II  Zeitsch.  f.  ang.  Chem.  (1909),  22,  1451-1459  and  1492-1502. 


276  THE  HYDROGENATION  OF  OILS 

of  26  to  28  per  cent,  while  in  a  sealed  tube,  the  reduction  proceeds  to 
the  extent  of  60  per  cent.  If  an  ethereal  solution  of  oleic  acid  be 
treated  with  palladium  black,  and  a  current  of  hydrogen  led  through, 
stearic  acid  can  be  detected  after  one-half  hour;  with  platinum  black 
under  similar  conditions,  24  per  cent  of  stearic  acid  is  obtained  after 
one-half  hour,  84.5  per  cent  after  3J  hours  and  90  per  cent  after  5 
hours.  Oleic  acid  is  also  reduced  by  nickel  and  cobalt  (prepared  from 
the  oxides),  in  presence  of  hydrogen,  at  temperatures  of  45°  to  184°  C. 
and  98°  to  250°  C.  respectively.* 

In  order  to  test  the  view  that  the  increased  reducing  power  of 
occluded  hydrogen  is  due  to  a  kind  of  physical  compression,  Fokin 
carried  out  a  series  of  experiments,  which  showed  that  compressed 
hydrogen  (up  to  a  pressure  of  35  atmospheres)  effected  the  reduction 
of  unsaturated  hydrocarbons  more  rapidly  and  completely  and  at 
lower  temperatures  than  hydrogen  at  atmospheric  pressure. f 

Hydrogen  reduces  certain  metals  from  their  solutions,  as,  for  instance,  silver 
from  an  aqueous  solution  of  the  nitrate.  The  action  of  hydrogen  on  metallic  solu- 
tions is  much  more  energetic  when  one  operates  under  pressure  as  has  been  observed 
by  Beketoff. 

In  connection  with  the  effect  of  hydrogen  on  metallic  catalysts  to  alter  the 
properties  of  the  metal,  a  discussion  appearing  in  the  Metallurgical  and  Chemical 
Engineering  (1913),  679,  on  the  "Passivity  of  Metals,"  is  of  interest.  According 
to  Foerster  and  also  Schmidt  a  metal  such  as  iron  is  passive  in  its  normal  condition 
and  only  becomes  active  under  the  influence  of  a  catalyst.  Hydrogen  is  stated  to 
have  this  catalytic  effect  and  hydrogen  ions  have  also  the  same  action.  Schmidt 
states  that  the  most  important  of  the  catalysts  which  overcome  the  passive  state 
of  metals  is  hydrogen  and  that  a  small  amount  of  it  can  activate  large  amounts  of 
iron,  nickel  and  chromium.  The  preparation  of  a  non-pyrophoric  catalyzer  of  the 
nickel  type  by  passing  carbon  dioxide  or  similar  gas  over  it  for  a  considerable  period 
may  perhaps  depend  on  the  elimination  of  the  hydrogen  which  permits  the  metal 
to  resume  its  normal  passive  state,  in  which  condition  exposure  to  the  air  does  not 
injure  the  catalytic  activity. 

Towards  hydrogen,  palladium  in  sheet  form  appears  to  be  both 
active  and  passive.  In  the  active  form  the  metal  will  rapidly  absorb 
large  amounts  of  the  gas,  while  in  the  passive  condition  only  slight 
amounts  are  occluded.  The  absorption  of  hydrogen  proceeds  in  two 
stages;  first,  a  rapid  occlusion  at  the  surface  and  second,  a  slow  ab- 
sorption into  the  metal  mass.t 

Sieverts,  Jurisch  and  Metz  §  have  further  investigated  the  solu- 
bility of  hydrogen  in  solid  alloys  of  palladium  with  gold,  silver  and 
platinum. 

*J.  S.  C.  I.,  1907,  1149. 

t  J.  S.  C.  I.,  1907,  169. 

JZeitsch.  phys.  Chem.  (1913),  513. 

§  Z.  anorg.  allgem.  Chem.,  322-62,  1915;    Chem.  Abs.,  1915,  3006. 


THE  OCCLUSION  OF  HYDROGEN  277 

Sieverts*  has  investigated  the  relationship  between  the  quantity  of  hydrogen 
absorbed  and  the  partial  pressure  between  138°  and  821°  C.  and  at  hydrogen 
pressures  between  1  and  760  mm.,  on  palladium.  With  both  commercial  and 
pure  palladium  wire,  between  the  temperature  limits  mentioned,  the  quantity 
of  hydrogen  absorbed,  Lp,  by  unit  weight  of  palladium  is  not  strictly  propor- 
tional to  the  square  root  of  the  hydrogen  pressure  p.  The  experimental  results 
are  better  expressed  by  the  equation,  Lp  =  k\p^-{-kzpj  in  which  ki  and  &;  are 
constants  depending  on  the  temperature;  the  equation  is  not  true  for  higher 
pressures.  This  expression  can  be  regarded  as  representing  that  the  hydrogen 
molecules  are  in  equilibrium  with  hydrogen  atoms,  both  in  solution  in  the  palla- 
dium and  in  the  gas  phase,  and  that  Henry's  law  holds  strictly  for  both  atoms 
and  molecules.  The  dissociation  constant  of  hydrogen  is  25  at  138°;  109  at 
315°;  112  at  619°,  and  102  at  821°  C.  The  quantity  of  hydrogen  absorbed  by 
unit  weight  of  palladium  depends  only  on  the  pressure  and  temperature,  and  is 
entirely  independent  of  the  surface  area  of  the  metal;  consequently,. the  absorp- 
tion of  hydrogen  by  palladium  is  to  be  regarded  as  a  true  solution  phenomenon. 
The  isothermals  of  palladium-black  and  palladium-sponge  are  similar  to  those 
of  compact  palladium,  but  the  actual  curves  differ  with  different  specimens,  and 
are  apparently  dependent  on  the  nature  of  the  palladium.  The  similarity  of  the 
absorption  isothermals  in  all  cases  indicates  that  in  palladium-black  and  palla- 
dium-sponge the  absorption  is  mainly  due  to  solution  of  the  hydrogen,  at  least 
at  temperatures  above  100°  C.  At  lower  temperatures  it  is,  however,  likely 
that  surface  absorption  accounts  for  a  large  portion  of  the  hydrogen  taken  up. 
The  above  results  are  in  strict  accord  with  the  statement  that  palladium-black 
and  palladium-sponge  are  made  up  of  varying  quantities  of  amorphous  and 
crystalline  palladium.  Both  modifications  appear  to  act  as  solvents  for  hydro- 
gen with  different  powers  of  solution. 

The  method  used  was  the  same  as  used  in  previous  work  by  Sieverts  with 
additional  precautions  to  ensure  accuracy.  The  alloys  were  studied  from  138°  to 
820°  and  with  hydrogen  pressures  of  one  atmosphere  and  less.  The  velocity 
of  the  absorption  and  the  relation  between  gas  pressure  and  amount  absorbed 
are  the  same  as  with  pure  metals.  For  all  three  series  of  alloys  the  amount  of 
hydrogen  absorbed  per  gram  of  alloy  is  approximately  proportional  to  \/PH 
and,  with  the  exception  of  alloys  rich  in  platinum,  at  constant  pressures  de- 
creases with  increasing  temperature.  With  increasing  amounts  of  platinum  the 
amount  of  hydrogen  absorbed  decreases  at  all  temperatures,  probably  reaching  a 
minimum  in  the  interval  50  to  100  per  cent  platinum.  The  higher  the  tempera- 
ture the  smaller  the  relative  solubility  lowering  with  constant  platinum  incre- 
ments; at  constant  temperatures  this  lowering  is  smaller  than  proportional  to 
the  platinum  content.  At  all  temperatures,  the  addition  of  silver  palladium 
increases  the  solubility  of  hydrogen  in  palladium,  until  a  maximum  is  reached 
at  40  per  cent  silver,  after  which  the  solubility  falls  off  rapidly,  the  effect  passing 
through  zero  between  50  and  70  per  cent  silver.  The  solubility  maximum  ob- 
tained with  40  to  50  per  cent  silver  increases  with  decreasing  temperature  from 
800°  to  270°,  then  decreases.  Addition  of  gold  to  palladium  has  an  effect  similar 
to  a  silver  addition,  although  not  so  pronounced.  At  827°  the  solubility  of 
hydrogen  is  diminished  by  addition  of  gold;  at  other  temperatures  it  increases 
to  a  maximum,  then  diminishes.  The  gold  concentration  corresponding  to  the 

*Z.  physik.  Chem.,  1914,  451-478.  J.  Chem.  Soc.,  1915,  268-269,  Chem.  Abs., 
1915,  12;  J.  S.  C.  I.,  1915,  664. 


278  THE   HYDROGENATION  OF  OILS 

maximum  solubility  decreases  with  increasing  temperature.  Between  830°  and 
220°  a  given  gold  content  results  in  a  greater  increase  in  solubility  the  lower  the 
temperature;  below  220°  the  relative  solubility  increase  probably  diminishes. 
The  curves  showing  the  variation  of  various  physical  properties  with  comparison 
in  each  of  the  binary  palladium  metal  systems  show  marked  similarities  with 
the  curves  of  hydrogen  absorption  in  that  system.  The  gold  and  silver  alloys 
are  marked  by  a  high  solvent  power  for  hydrogen  as  well  as  by  unusual  electrical 
properties.  All  the  evidence  points  to  the  formation  of  true  ternary  solid  solu- 
tions between  hydrogen  and  the  binary  alloys. 

Observations  (at  25°  C.)  have  been  made  by  Smith  and  Martin  *  of  the  change 
of  electrical  resistance  and  cathode  potential  of  palladium  wires  during  their 
cathodic  occlusion  of  hydrogen  evolved  from  nitro  sulphonic  acid  and  after  the 
interruption  of  electrolysis.  All  of  the  palladium  wires  increased  in  resistance 
by  more  than  56  per  cent,  finally  reaching  a  value  which  remained  unaltered 
by  prolonged  charging,  but  which  varied  irregularly  from  wire  to  wire.  With 
small  wires  and  ribbon  (less  than  0.1  mm.  diameter)  there  was  a  further  increase 
in  resistance  after  the  interruption  of  electrolysis,  and  a  change  of  resistance 
whenever  the  charging  current  was  changed,  but  these  effects  were  not  found 
with  larger  wires  (0.32  mm.).  The  resistance  of  the  saturated  wire  (less  than 
0.1  mm.  diameter)  observed  during  momentary  interruptions  of  the  electrolysis 
varied  in  a  well-defined  manner  with  the  polarizing  current,  and  the  resistance 
after  the  interruption  of  the  electrolysis  undergoes  changes  which  are  reversible 
and  reproducible.  Considerations  are  given  which  make  it  probable  that  the 
changes  of  resistance  in  the  smaller  wires  are  due  to  processes  occurring  within 
the  metal,  and  not  far  removed  from  its  surface,  and  the  tentative  conclusion  is 
suggested  that  hydrogen  occluded  at  the  cathode  surface  exists  for  some  time 
in  a  transitional  state  in  which  it  possesses  an  electrical  conductivity  of  its  own, 
and  passes  gradually  into  another  form  in  which  it  has  much  less  conductance, 
or  none.  A  few  experiments  on  copper  wires,  and  a  single  exception  on  a  nickel 
wire,  show  that  these  metals  do  not  suffer  any  measurable  change  of  electrical 
resistance  under  conditions  which  produce  a  high  degree  of  occlusion  in  pa  ladium. 

Stahl  f  has  investigated  the  solubility  of  gases  in  mo'ten  copper,  and  states 
that  the  evidence  of  the  solubility  of  hydrogen  is  given  by  the  surface  disin- 
tegration and  blister-like  structure  assumed  by  the  metal  during  solidification 
after  exposure  to  this  gas.  An  absorption  of  hydrogen  and  diffusion  through 
copper  has  been  detected  at  650°  C.  Up  to  1500°  C.,  the  absorption  increases 
almost  linearly  with  the  temperature,  except  at  the  melting-point  of  the  metal, 
when  a  sudden  increase  occurs.  At  650°  the  solubility  is  0.1  and  at  1500°  C., 
1.4  milligrams  of  hydrogen  per  100  g.  of  copper.  With  both  the  molten  and  solid 
metal,  the  solubility  increases  as  the  square  root  of  the  pressure.  The  conduc- 
tivity of  copper  is  not  affected  by  dissolved  hydrogen.  On  heating  copper  con- 
taining oxide  in  a  hydrogen  atmosphere,  the  gas  penetrates  the  metal  and 
reduces  the  oxide  with  formation  of  water,  which  escapes  by  disintegrating  the 
metal  and  rendering  it  unsuitable  for  further  mechanical  working.  A  reaction 
of  this  nature  takes  place  in  molten  copper  during  the  "  polling  "  treatment. 

Hydrocarbons  are  decomposed  by  molten  copper  into  carbon  and  hydrogen, 
of  which  the  former  and  the  latter  absorbed.  No  occlusion  of  any  undecom posed 
hydrocarbon  has  been  observed. 

*  J.  Am.  Chem.  Soc.,  38,  2577-94,  1916;    Chem.  Abs.,  1917,  8. 
t  J.  S.  C.  I.,  1914,  1159. 


THE  OCCLUSION  OF  HYDROGEN  279 

The  solubility  of  hydrogen  and  nitrogen  in  iron  has  been  investigated  by 
Jurisch  *  100  g.  of  iron  wire  with  0.04  per  cent  carbon  were  heated  in  a  quartz 
bulb  and  the  absorption  of  hydrogen  measured  at  different  temperatures.  Be- 
tween 416°  and  1450°,  the  solubility  of  hydrogen  in  iron  increases  with  rising 
temperature,  at  the  former  temperature  0.035  milligram  of  hydrogen  is  ab- 
sorbed and  at  the  latter  1.08  milligrams.  Between  850°  and  900°  an  abnormal 
absorption  was  noticed  owing  to  the  reaction  between  the  trace  of  carbon  present 
and  hydrogen  to  form  methane,  whereby  the  carbon  content  of  the  iron  was 
reduced  to  0.02  per  cent.  When  slowly  cooled  only  0.01  milligram  of  hydrogen 
remained  with  the  iron.  Experiments  with  reduced  iron  powder  previously 
heated  for  nine  hours  in  hydrogen  showed  that  the  maximum  nitrogen  absorp- 
tion took  place  at  930°  when  21.65  milligrams  were  absorbed.  At  878°  only 
1.58  milligrams  of  nitrogen  were  absorbed  and  above  930°  the  absorption  grew 
gradually  smaller.  The  above  data  refer  to  hydrogen  and  nitrogen  at  ordinary 
atmospheric  pressure. 

Joukoff  t  states  that  when  cerium  is  heated  in  an  atmosphere  of  hydrogen  it 
rapidly  absorbs  the  gas  at  about  350°  C.  Between  450°  and  510°  C.  the  dis- 
sociation pressure  was  about  1  millimeter  so  long  as  the  proportion  of  hydrogen 
did  not  exceed  that  corresponding  to  cerium  hydride;  beyond  this  the  disso- 
ciation pressure  increased  with  the  hydrogen  concentration.  It  is  concluded 
that  the  hydride  is  formed,  and  that  this  hydride  is  capable  of  dissolving 
hydrogen. 

Theoretical  considerations  on  hydrogenation  on  the  basis  of  velocity  measure- 
ments made  on  the  hydrogenation  of  fumaric  acid  with  palladium  sol  as  cat- 
lyzer  are  discussed  by  Korevaar  J  in  a  preliminary  paper,  containing  no  experi- 
mental results.  The  rate  of  hydrogenation  of  fumaric  acid  in  the  presence  of 
palladium  sol  is  in  accordance  with  Nernst's  surface  film  theory  of  heterogeneous 
reactions.  The  velocity  was  found  to  increase  as  the  two-thirds  power  of  the  rate  of 
stirring,  and  the  temperature  coefficient  per  10°  was  1.25,  instead  of  1.7,  the 
theoretical  for  microheterogeneous  systems.  With  small  concentration  of  palla- 
dium sol,  doubling  the  amount  of  sol  more  than  doubled  the  rate  of  hydrogena- 
tion; this  has  been  explained  by  Bredig  as  a  common  property  of  microhetero- 
geneous systems  due  to  increased  Brownian  movement.  Since,  in  systems  of 
this  type,  the  apparent  rate  of  the  reaction  is  determined  by  the  diffusion  of 
the  reacting  molecules  through  the  stationary  film,  at  high  initial  concentration 
of  fumaric  acid  the  rate  should  be  determined  by  the  rate  of  diffusion  of  the 
hydrogen,  and  hence  should  be  constant;  when  the  concentration  of  fumaric 
acid  decreases  below  a  value  determined  by  the  hydrogen  concentration  and  the 
ratio  between  the  diffusion  constants  of  the  two  molecular  species,  the  rate 
should  be  determined  by  the  diffusion  of  fumaric  acid,  and  hence  should  be  that 
of  a  first  order  reaction.  This  is  in  harmony  with  the  experiments. 

Unsaturated  acids  of  the  olefin  series  have  been  reduced  electro- 
lytically  under  similar  conditions  and  their  arrangement,  according 
to  ease  of  hydrogenation  determined  by  Pomilio.§  The  reductions 

*Inaug.  Dissert.  Leipsic,  1912;    Chem.  Abs.,  1915,  286. 

t  J.  Russ.  Phys.  Chem.  Soc.,  1914,  2073,  Bull.  Soc.  Chim.,  1914,  531;  J.  S.  C.  I., 
1914,  1206;  Chem.  Abs.,  1915,  566. 

JChem.  Weekblad,   13,  98-107,   1916;    Chem.  Abs.,   1916,   1002. 
§Z.  Electrochem.,   1915,  21,  444;    Chem.  Abs.,  1916,  2576. 


280  THE  HYDROGENATION  OF  OILS 

were  carried  out  in  both  aqueous  and  alcoholic  solutions  of  sul- 
phuric acid,  using  a  nickel  gauze  cathode  impregnated  with  spongy 
nickel  and  a  platinum  anode.  The  current  employed  was  0.5  ampere 
and  the  temperature  ranged  from  25°  to  90°.  Electrolysis  was 
carried  on  for  six  to  twenty-four  hours.  In  this  way  the  rates  of 
reduction  of  crotonic,  allylacetic,  undecylic,  oleic,  erucic,  linoleic, 
linolenic,  fumaric,  maleic,  mesaconic,  citraconic,  itaconic,  allylma- 
lonic  and  aconitic  acid  have  been  examined  and  the  results  tabulated 
graphically.  The  curves  obtained  show  that  the  speed  of  hydro- 
genation  depends  both  on  the  solvent  and  the  nature  of  the  acid. 
The  most  easily  reduced  acid  is  maleic;  in  the  class  of  moderately 
easily  reducible  acids  are  placed  citraconic  and  related  acids,  while 
the  higher  members  of  the  series,  insoluble  in  water,  like  oleic  acid, 
are  classified  as  difficultly  reducible.  Oleic  acid,  in  fact,  is  reduced 
only  very  slowly  either  in  aqueous  suspension,  aqueous  or  alcoholic 
soap  solutions,  or  in  turkey  red  oil,  using  a  large  variety  of  metals 
as  cathodes  50  cc.  of  this  acid  in  0.2  H2SO4  at  70°  with  a  Ni  cathode 
gave  only  9.0  g.  of  stearic  acid  after  ten  hours.  Erucic,  ricinoleic 
and  linolenic  acids  all  showed  little  or  no  reduction  when  treated 
electrolytically.  Of  the  higher  unsaturated  acids  linolic  is  most  easily 
educed,  proof,  according  to  Pomilio  that  the  C:C  and  C:O  groups 
are  in  close  proximity,  assuming  with  Thiele  that  the  reactivity 
depends  on  the  relative  position  of  these  double  unions. 

On  the  assumption  that,  during  the  absorption  of  hydrogen,  this  gas  and  the 
unsaturated  substance  traverse  a  layer  surrounding  the  particles  of  the  catalyst 
and  that,  consequently,  the  medium  should  exert  a  marked  influence  on  the  rate 
of  absorption,  Boeseken  and  Bilheimer.*  have  measured  the  rate  of  reduction 
of  pinene  in  various  solvents  with  a  view  of  obtaining  data  concerning  this  influ- 
ence. In  formic  acid  or  absolute  alcohol  the  absorption  proceeded  very  slowly 
and  the  activity  of  the  catalyst  was  seriously  impaired;  in  anhydrous  ether  the 
rate  of  the  absorption  was  diminished  but  the  activity  of  the  platinum  was  not 
decreased.  When  ethyl  acetate  was  used  as  the  solvent  the  absorption  pro- 
ceeded regularly  at  first,  then  decreased  and  practically  stopped,  but  the  activity 
of  the  platinum  was  not  affected.  With  acetic  acid  the  rate  of  absorption  de- 
creased without  the  catalyst  losing  its  activity,  and  similar  results  were  observed 
in  the  case  of  propionic,  butyric,  isobutyric,  and  iso valeric  acids. 

*  Rec.  Trav.  Chim.  Pays-Bas.,  1916,  35  288-298;  J.  S.  C.  I.,  1916,  487. 


CHAPTER    XII 
THE  ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS* 

The  hydrogenation  of  oils  has  to  such  an  extent  changed  certain  of 
the  constants  by  which  oils  and  fats  are  at  least  in  part  identified, 
namely,  the  iodine  number  and  the  specific  gravity,  that  the  identifi- 
cation of  a  fat  or  fatty  mixtures,  often  heretofore  a  troublesome  matter 
at  best,  now  promises  to  become  even  more  difficult. 

The  reduction  of  the  iodine  number  through  the  introduction  of 
hydrogen  into  the  oil,  in  a  sense,  is  arbitrary;  there  is  no  difficulty  in 
reducing  the  iodine  number  almost  to  zero  through  the  hydrogenation 
process,  or  at  any  moment  to  interrupt  the  operation  and  from  one  and 
the  same  initial  material  to  produce  products  having  the  most  varied 
iodine  numbers. 

The  specific  gravity  and  melting  point  advance  hand  in  hand  as 
saturation  progresses,  the  specific  gravity  approaching  that  of  tri- 
stearin, while  the  resultant  melting  point  in  considerable  measure  de- 
pends upon  the  molecular  weight  and  the  hydroxyl  content  of  the 
fatty  acid  components  of  the  oil.  The  specific  gravity  of  a  hardened 
cottonseed  oil  whose  iodine  number  had  been  reduced  to  zero  was 
found  by  Normann  and  Hugel  f  to  be  0.9999  at  15°  C.,  while  they  note 
that  tristearin  has  a  specific  gravity  of  1.0101  at  the  same  temper- 
ature.J 

The  index  of  refraction  also  is  strongly  modified.  A  sample  of  fish 
oil  at  56°  C.,  according  to  Normann  and  Hugel,  showed  a  figure  of 
53.8;  while  after  hardening  to  an  iodine  number  of  22.5  the  index  was 
36°  C.  at  the  same  temperature.  (Scale  of  the  Zeiss  butter  refrac- 
tometer.) 

Observations  made  in  the  author's  laboratory  on  the  index  of  re- 
fraction of  a  number  of  hydrogenated  oils  gave  the  results  noted 
below :  § 

*  Jour.  Ind.  Eng.  Chem.  (1914),  117. 

t  Chem.  Ztg.  (1913),  815. 

I  The  specific  gravity  of  tristearin  is  given  by  the  Chemiker  Kalender  as  1.0101 
at  15°  C.,  while  Lewkowitsch  reports  the  specific  gravity  of  a  specimen  of  not  quite 
pure  stearin  in  the  melted  state  as  0.9235  at  65.5°  C. 

§  A  sample  of  hydrogenated  cottonseed  oil  used  extensively  in  this  country 
exhibited  a  refractive  index  of  1.4492  and  a  melting  point  of  59.9°  C. 

281 


282 


THE  HYDROGENATION  OF  OILS 


INDEX  OF  REFRACTION  AT  55' 

(Abbe  Refractometer  *) 


C. 


Original  oil 

Hydrogenated  oil 

Corn   .                 .               '.  .  .  .  . 

1.4615 

1.4514  (M.  P.  55  7°  C.) 

Whale  (No   1) 

1  4603 

1  4550  (M   P  41  5°  C  ) 

Soya  bean  

1.4617 

1.4538  (M.  P.  50.3°  C.) 

Cocoanut  oil  ('"olein") 

1  4429 

1  4425  (M   P  24  7°  C  ) 

Linseed 

1  .  4730 

1  4610  (M   P  42  3°  C  ) 

Palm 

1.4523 

1  4517  (M.  P.  38  7°  C.) 

Palm                                                  

1  .  4523 

1.4494  (M.  P.  44  8°  C.) 

Peanut  (edible)  .  . 

1.4567 

1.4547  (M.  P.  34.7°  C.) 

It  is  of  interest  to  note  that  while  the  addition  of  hydrogen  to  fatty 
oils  reduces  the  index  of  refraction,  the  addition  of  oxygen  increases  the 
index  as  is  shown  in  the  case  of  blown  or  ozonized  oils. 

The  gradual  reduction  of  the  index  of  refraction  by  progressive 
hydrogenation  is  shown  in  the  following  table  compiled  from  deter- 
minations made  in  the  author's  laboratory. 

Cottonseed  oil  was  hydrogenated  for  a  period  of  ten  hours  and 
samples  were  drawn  at  one-hour  intervals. 


Melting  point 

Index  of  refraction, 
55°  C. 

Original  oil  

1   4588 

1  hour  

28.2°  C. 

1  4577 

2  hours  

31.3 

1  .  4568 

3  hours 

34  3 

1  4557 

4  hours 

37  9 

1  4549 

5  hours                .                             .      . 

40  8 

1  4540 

6  hours           

43  8 

1  4527 

7  hours  

45.6 

1  4518 

8  hours  

47.3 

1.4510 

10  hours  

55.9 

1.4496 

The  saponification  number  practically  does  not  change.  The  con- 
tent of  free  fatty  acids  changes  but  little.  A  sample  of  cottonseed  oil 
containing  1.8  per  cent  fatty  acid  was  found,  after  hardening  to 
various  degrees,  to  have  a  fatty  acid  content  ranging  from  1.4  per  cent 
to  1.9  per  cent.  With  sesame  oil  containing  2.44  per  cent  fatty  acid 
the  resulting  hardened  oil  contained  2.55  per  cent  of  acid.  The  con- 
tent of  unsaponifiable  bodies  does  not  essentially  change.  Cotton- 
seed oil  having  0.55  per  cent  unsaponifiable  matter,  after  hardening, 

*  Refraction  values  are  given  in  terms  of  true  refractive  index  and  also  according 
to  the  arbitrary  scale  of  the  butyro  refractometer,  in  order  to  follow  the  data  avail- 
able, as  rendered. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      283 


showed  a  content  of  unsaponifiable  bodies  ranging  from  0.45  per  cent 
to  0.55  per  cent;  sesame  oil  with  aii  unsaponifiable  content  of  0.70 
per  cent,  after  hardening,  (gontained  0.85  per  cent  unsaponifiable. 

Cholesterol  and  phytosterol,  according  to  Bomer,  are  not  changed 
by  treating  oils  with  hydrogen,  although  this  is  somewhat  contrary 
to  the  statement  of  Windaus,*  according  to  whom  cholesterol  may  be 
easily  reduced  by  the  catalytic  process.  Willstatter  and  Mayer  f 
hydrogenated  cholesterol  in  ether  solution  with  a  platinum  catalyzer. 

An  examination  of  the  unsaponifiable  constituents  of  several  hardened 
oils  has  been  made  by  Marcusson  and  MeyerheimJ  who  used  the  digi- 
.tonin  method  for  the  separation  of  sterol.  The  following  table  gives 
the  results  obtained. 

UNSAPONIFIABLE  CONSTITUENTS  OF  HARDENED  OILS 


Total 
unsap- 
onifi- 
able 
matter 

Sterol 
obtained 
by  digi- 
tonin 
method 

Sterol-free  unsaponifiable 
components 

Per 

cent 

w* 

Per 

cent 

Per 

cent 

;NJ> 

Iodine 
number 

Cottonseed  oil  (solidifying  point  32°  C.) 
Cottonseed  oil  (solidifying  point  38°  C.) 
Linseed  oil 

0.7 
0.6 
1.0 
0.3 
0.9 
0.9 
0.8 
0.7 

-  5.8 
±  0 
+19.5 
-10.1 
-  1.9 
-  3.3 
+  4.7 
+  1.4 

0.22 
0.14 
0.21 
0.13 
0.10 
0.07 
0.05 
0.024 

0.4 
0.4 
0.7 
0.19 
0.7 
0.7 
0.7 
0.64 

+  6.8 
+  8.1 
+19 
+  5.2 
+  1.3 

+  'i.'8 

+  2.8 

85" 
56!  i 

Castor  oil 

Talgol  

Talgol  extra 

Candelite 

Candelite  extra 

The  examination  showed  that  the  sterol  content  of  hardened  fats  is 
slightly  less  than  that  of  the  corresponding  natural  fat  or  oil.  The 
cottonseed  oil  first  listed  was  prepared  by  the  Wilbuschewitsch  process 
at  150  to  160°  C.  with  hydrogen  under  pressure.  The  second  sample 
of  the  cottonseed  oil  was  made  by  the  Normann  process,  presumably 
at  a  higher  temperature  but  without  pressure.  At  temperatures  of 
150  to  160°  C.  apparently  the  difficultly  reducible  sterol  is  not  affected 
by  hydrogen  and  Marcusson  and  Meyerheim  call  attention  to  the 
observations  of  Adamla  §  who  could  not  hydrogenate  cholesterol  with  a 

*  Ber.  d.  chem.  Ges.  (1912),  3051. 

t  Willstatter  and  Mayer  converted  cholesterol  quantitatively  into  dihydro- 
cholesterol  by  passing  a  slow  stream  of  hydrogen  for  two  days  through  an  ethereal 
solution  of  cholesterol  in  the  presence  of  platinum  black  (Ber.,  1908  (41),  2199). 
(See  U.  S.  Patent  to  Ellis,  1,086,357,  Feb.  10,  1914.) 

t  Zeitsch.  f.  angew.  Chem.,  1914:  27,  201. 

§  Dissertation.     Beitrage  zur  Kenntnis  des  Cholesterins,  Freiburg,  1911,  12. 


284 


THE  HYDROGENATION  OF  OILS 


nickel  catalyzer  at  temperatures  below  170°  C.  Marcusson  and  Meyer- 
heim  found  cholesterol  to  hydrogenate  readily  at  195°  C.  while  phytos- 
terol  was  practically  unchanged  after  treatment  with  hydrogen  at 
200°  C.  From  these  and  other  tests  it  was  found  that  cholesterol  is 
much  less  resistant  than  phytosterol  to  the  action  of  hydrogen. 

The  content  of  sterol  decreases  with  increasing  melting  point  as  shown 
by  the  following  table. 


Hydrogenated  oil 

Iodine 
number 

Solidifying 
point 

Sterol 
content 

Whale  oil  (not  hydrogenated) 

114 

0  13 

Talgol 

67 

31 

0  10 

Talgol  extra  

36 

38 

0  07 

Candelite  

20 

42 

0.05 

Candelite  extra 

13 

45 

0  02 

The  unsaponifiable  constituents  of  hardened  fat  when  freed  from 
sterols  were  of  light  yellow  color  and  of  salve-like  consistency.  These 
sterol-free  bodies  obtained  from  Talgol,  Talgol  extra,  Candelite  and 
Candelite  extra,  when  recrystallized  from  benzine,  yielded  a  product 
melting  between  59.3°  and  59.8°,  which  proved  to  be  a  fatty  alcohol, 
probably  octodecyl  alcohol. 

In  the  case  of  the  acetyl  number  more  noticeable  changes  take  place 
according  to  Normann  and  Hugel.  When  hardening  castor  oil,  for 
example,  the  hydroxyl  number  in  one  sample  dropped  from  156  to  102; 
in  another  sample  the  number  fell  to  131.  The  hydroxyl  group  is  thus 
more  or  less  broken  down  by  the  hydrogenation  process,  at  least  under 
some  conditions  of  treatment. 

HYDROGENATED   CASTOR  OIL 

Acid  number 3.5 

Saponification  number 183 . 5 

Iodine  number 4.8 

Acetyl  number 153 . 5 

Acetyl  number  of  the  fatty  acids 143 . 1 

Acid  number  of  the  fatty  acids 184 .5 

Saponification  number  of  the  fatty  acids •. 187 . 9 

Melting  point  of  the  fat 68°  C. 


Melting  point  of  the  fatty  acids 


70°  C. 


Melting  point  of  the  acetylated  acids 47°  C. 

The  properties  of  hardened  castor  oil  have  been  noted  by  Garth* 
whose  observations  differ  somewhat  from  those  of  Normann  and 
Hugel.     As  is  generally  known,  castor  oil  differs  materially  from  many 
*  Seifen.  Ztg.  (1912),  1309. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      285 

other  common  oils  in  such  respects  as  its  high  viscosity,  solubility  in 
alcohol  and  difficulty  of  salting  out  its  soaps  by  electrolytes.  Hard- 
ened castor  oil  dissolves  in  alcohol  only  by  heating  and  separates  on 
cooling,  but  is  soluble  at  ordinary  temperature  in  chloroform.  The 
constants  of  one  sample  of  hardened  castor  oil  examined  by  Garth  are 
given  in  the  above  table. 

These  results  obtained  by  Garth  would  indicate  that  the  saponifi- 
cation  and  acetyl  number  do  not  change.  The  iodine  number  has 
fallen  greatly  and  the  melting  point  is  much  increased.  The  differ- 
ence between  the  acid  number  of  the  fatty  acids  and  their  saponifica- 
tion  number  points  to  the  formation  of  lactones.  As  is  known  castor 
oil  has  the  property  at  high  temperatures  of  forming  anhydrides, 
accompanied  by  polymerization. 

The  effect  of  hydrogenation  on  color  tests  of  oils  is  variable.  Thus 
the  Boudouin  sesame  oil  test  is  not  influenced;  in  fact  the  reaction 
seemingly  is  sharper  after  treatment  of  the  oil  with  hydrogen,  while 
the  Halphen  test  is  not  likely  to  give  positive  results  even  with  oils 
which  have  been  only  slightly  hardened. 

The  Becci  test  is  operative  with  slightly-hardened  cottonseed  oil, 
but  is  indistinct  with  highly-hardened  oil  so  that  this  test  is  significant 
only  in  event  of  a  positive  coloration. 

Hardened  fish  oil  loses  all  its  essential  characteristics,  such  as  the 
formation  of  well-defined  bromine  compounds  of  the  higher  unsatu- 
rated  fatty  acids.  Thus  there  are  obtained  after  hardening,  new  fatty 
acids  corresponding  to  the  saturated  bodies,  arachidic  (C2oH40O2)  and 
behenic  (CjaH^C^)  acids,  which  in  variable  amounts  up  to  a  proportion 
of  20  per  cent  and  more  have  been  observed  in  certain  hydrogenated 
oils.  In  the  hardening  of  rape  oil  behenic  acid  is  formed  from  the 
erucic  acid  present.  Other  oils  or  fats  with  a  noticeable  proportion  of 
acids  with  more  than  18  carbon  atoms  in  the  molecule  apparently 
scarcely  ever  come  into  the  trade. 

The  complete  conversion  of  erucic  acid  to  behenic  acid  is  readily 
obtained  by  reducing  with  hydrogen  in  the  presence  of  nickel.  This 
method  has  been  used  by  Lewkowitsch  in  the  determination  of  erucic 
acid.* 

The  saturated  fatty  acids  obtained  by  the  hydrogenation  of  the  un- 
saturated  acids  of  Japanese  sardine  oil  were  found  by  Majima  and 
Okada  f  to  have  a  melting  point  of  75°  C.  and  a  molecular  weight  of 
349,  and  consisted  in  the  main  of  the  higher  homologues  of  stearic 
acid,  such  as  C2oH40O2  or  C^H^C^.  Similar  results  were  obtained  on 


*  Lewkowitsch,  Oils,  Fats  and  Waxes,  5th  edition,  Vol.  I,  195  and  553. 
f  J.  S.  C.  I.,  1914,  362. 


286  THE  HYDROGENATION  OF  OILS 

hydrogenating  the  more  fluid  fatty  acids  obtained  by  chilling  and 
pressing. 

As  a  test  for  hydrogenated  peanut  oil,  Kreiss  and  Roth  *  have  given 
a  method  which  consists  in  saponifying  20  grams  of  the  oil  with  40  cc. 
of  alcoholic  potash;  then  adding  60  cc.  of  alcohol  and  acidifying  by 
the  addition  of  50  per  cent  acetic  acid  of  which  approximately  15  cc. 
are  required.  One  and  one-half  grams  of  lead  acetate  are  added  and 
the  mixture  allowed  to  stand  overnight.  The  lead  salts  which  sepa- 
rate are  decomposed  by  boiling  with  5  per  cent  hydrochloric  acid,  the 
fatty  acids  are  dissolved  in  50  cc.  of  90  per  cent  alcohol  with  slight 
warming  and  the  solution  is  placed  in  water  at  15  degrees  for  about 
one-half  hour.  The  crystals  which  separate  are  recrystallized  from 
25  cc.,  then  12J  cc.  of  90  per  cent  alcohol  and  the  melting  point  deter- 
mined. The  presence  of  at  least  5  per  cent  arachidic  acid  causes  the 
melting  point  of  the  third  crystallization  to  be  over  70°  C. 

Normann  and  Hugelf  state  that  this  test  is  applicable  likewise  to 
hardened  fish  and  rape  oil.  They  tested  a  number  of  samples  of  fish 
oil  from  several  sources  and  found  in  each  case  that  the  melting  point 
of  the  recrystallized  fatty  acids  was  at  least  70  degrees.  Normann  and 
Hugel  also  state  that  it  is  unnecessary  with  hardened  fish  oil  to  allow 
the  lead  acetate  to  react  for  several  hours,  it  sufficing  simply  to  let  the 
mixture  stand  until  cooled  to  room  temperature;  this  can  be  hastened 
by  cooling  with  water.  So  large  a  proportion  of  fatty  acids  is  obtained 
according  to  this  procedure  that  the  specified  amount  of  alcohol  is  not 
sufficient  to  dissolve  them.  It  is  better  to  use  100  to  150  cc.  of  alcohol 
and  heat  on  the  water  bath  until  solution  is  affected.  The  application 
of  heat  should  not  be  continued  for  any  great  length  of  time  as  arachidic 
acid  readily  forms  esters.  The  mixture  is  then  placed  in  cold  water, 
cooled  to  room  temperature  and  the  separated  material  collected  and 
crystallized  several  times  from  alcohol  used  in  progressively  diminish- 
ing proportions.  Three  crystallizations  suffice  for  only  slightly  hard- 
ened fats.  With  fats  of  higher  consistency  one  must  recrystallize 
several  times  more  until  the  melting  point  is  constant. 

In  one  case  using  hardened  fish  oil  having  a  melting  point  of  44, 
three  recrystallizations  from  alcohol  gave  a  constant  melting  point  of 
only  63  degrees,  while  further  recrystallization  using  acetone  caused 
the  melting  point  to  advance  to  76  degrees.  In  doubtful  cases  one 
should  try  several  solvent  mediums.  If  the  melting  point  is  found  to 
be  above  70°  C.  Normann  and  Hugel  think  it  proof  that  either  hard- 
ened fish,  rape  or  peanut  oil  is  present.  If  one  is  certain  of  the  unitary 

*  Chem.  Ztg.  (1913),  58  and  369. 
t  Ibid.  (1913),  815. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      287 


character  of  the  oil  then  peanut  and  rape  oil  can  be  distinguished  from 
fish  oil  by  the  cholesterol  test,  provided  the  statement  of  Bomer  in 
regard  to  the  unchangeability  of  cholesterol  and  phytosteroi  under 
ordinary  conditions  of  oil  hydrogenation  is  confirmed. 

Data  on  hardened  oils  by  Davidsohn*  are  tabulated  below: 


M.  P. 

Acid 
number 

Saponifi- 
cation 
number 

Moisture 

Ash 

Talgol 

39  3 

3  4 

191   0 

0   10 

0  07 

Talgol  extra 

46  5 

3  5 

191   3 

0  13 

0  05 

Candelite 

49  0 

3.2 

191.0 

0  20 

0  08 

Candelite  extra 

51.9 

3.9 

190.8 

0.15 

0  04 

Coryphol 

79.3 

3.3 

189.9 

0.18 

0  05 

These  hardened  fish  oils  or  other  hardened  oils  put  out  under  the 
trade  names  indicated  are  manufactured  by  the  Germania  Oil  Works 
of  Emmerich. 

Knappf  states  that  the  attention  of  analysts  should  be  directed  to 
the  fact  that  in  the  immediate  future  they  will  be  called  upon  to  ana- 
lyze certain  new  artificial  fats  prepared  by  hydrogenation  and,  not 
improbably,  to  detect  their  presence  as  adulterants.  Thus,  for  ex- 
ample, starting  with  olive  oil,  as  the  absorption  of  hydrogen  proceeds, 
a  turbid  oil,  then  a  liquid  magma,  then  a  soft  fat  and  finally  a  hard 
fat  is  obtained.  Knapp  observes,  "  A  similar  change  occurs  with  all 
oils  containing  glycerides  of  unsaturated  acids.  This  rise  in  the  melt- 
ing point  is  naturally  accompanied  by  a  decrease  in  the  iodine  value 
and  refractive  index.  Fats  have  been  prepared  in  this  way  from  cot- 
tonseed oil  with  iodine  values  as  low  as  5,  and  if  desired  the  iodine 
value  could  doubtless  be  reduced  to  0,  and  the  melting  point  raised  to 
60°  or  70°  C.  While  it  is  too  costly  for  commercial  purposes  to  carry 
the  saturation  of  the  unsaturated  glycerides  to  completion,  it  might 
be  of  value  in  the  laboratory  as  an  aid  to  determining  the  component 
glycerides  in  a  pure  oil.  Not  only  the  oils  containing  glycerides  of 
oleic  acid  can  be  hardened,  but  also  those  containing  glycerides  of 
linolic  acid  and  linoleic  acid  (the  drying  oils),  and  even  of  such  highly 
unsaturated  acids  as  clupanodonic  (in  whale  oils).  Anyone  who  has 
seen  a  malodorous  oil  converted  into  a  bland  odorless  tallow  realizes 
the  commercial  possibilities  of  the  process.  And  when  it  is  remem- 
bered that  the  process  can  be  stopped  when  the  iodine  value  reaches 
a  desired  number,  the  possibility  becomes  evident  of  the  preparation 

*  Org.  f.  d.  Ol-und  Fetthdl.  (1913),  Nos.  14  and  15,  and  Seifen.  Ztg.  (1913),  529. 
t  The  Analyst  (1913),  102. 


288 


THE  HYDROGENATION  OF  OILS 


of  a  fat  with  any  required  analytical  figures."    In  support  of  the  fore- 
going, Knapp  furnishes  the  following  data: 


Hardened  oils 

Appearance 

Clear  liquid 

Solid  particles 
floating 

Soft  greasy 
solid 

Brittle  solid 

Butyro-refractometer    (cor- 
rected to  40°  C.) 

57  7 

47  7 

Fatty  acids: 
Iodine  value 

110 

94 

55 

22 

Titer 

34.7°  C. 

37  0°  C. 

42  5°  C. 

52  2°  C. 

Neutralization  value: 
(me.  KOH) 

197 

196 

196 

192 

The  analyst  is  chiefly  interested  in  the  question  of  how  these  fats 
are  to  be  detected.  It  is  doubtful  if  their  most  characteristic  feature, 
the  relatively  high  percentage  of  stearic  glycerides  which  they  contain, 
will  be  of  much  service.  Knapp  states  that  until  the  manufacturer 
accomplishes  the  difficult  step  of  completely  removing  the  nickel,  the 
detection  of  traces  of  this  metal  will  be  the  simplest  and  most  reliable 
test  for  hardened  oils.*  Although  the  catalyst  is  very  finely  divided, 
the  manufacturer  can  obtain  a  perfectly  clear  fat  by  careful  filtration, 
and  hence  it  is  the  nickel  contained  in  the  nickel  soaps  formed  by  the 
free  fatty  acids  present  that  one  has  to  detect.  The  following  method 
is  suggested :  50  grams  of  the  fat  are  heated  in  a  flask  with  20  cc.  hydro- 
chloric acid,  with  continued  vigorous  shaking.  The  mixture  is  allowed 
to  separate  while  hot,  and  part  of  the  acid  solution  is  evaporated  to 
dryness,  dissolved  in  a  drop  of  water  and  placed  on  a  white  tile.  One 
drop  of  ammonium  sulfide  is  added  to  this  and  also  to  a  drop  of  water 
for  comparison.  Knapp,  however,  tried  this  test  only  on  a  few  hard- 
ened oils,  and  in  some  cases  with  negative  results.  Dimethylglyoxime 
is  a  much  more  delicate  test,  but  unfortunately  Prall  has  found  f  that 
certain  pure  untreated  oils  give  a  red  coloration.  Hence  further 
investigation  is  needed. 

One  of  the  most  characteristic  tests  for  fish  oils  —  the  bromide 
estimation  —  is  quantitatively  useless  for  these  oils  after  hardening, 

*  Too  much  reliance  should  not  be  placed  on  the  nickel  test  as  evidencing  the 
presence  or  absence  of  hydrogenated  oils.  It  is  known  to  the  writer  that  hardened 
oils  which  are  free  from  nickel  are  on  the  market,  these  in  some  cases  presumably 
having  been  prepared  with  the  aid  of  palladium  as  a  catalyzer. 

f  Bomer,  Zeitsch.  Untersuch.  Nahr.  Genussn,  (1912),  24,  104,  and  Analyst  (1912), 
37,  452. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS     280 


as  the  percentage  of  ether-insoluble  brominated  glycerides  is  greatly 
reduced  thereby.  Not  only  are  the  analytical  figures  for  the  oils 
altered  by  this  absorption  of  hydrogen,  but  also  the  traces  of  substances 
which  often  serve  as  a  useful  test  for  the  particular  oil  in  which  they 
occur  —  e.g.,  Halphen's  reaction.  Knapp  believes  Bomer's  observa- 
tion that  phytosterol  and  cholesterol  are  not  changed  in  this  process 
is  of  great  analytical  value. 

Three  fats  obtained  by  Knapp  from  a  clear  cottonseed  oil,  hardened 
by  hydrogen  with  the  help  of  different  catalysts,  gave  the  following 
figures : 


Catalyst 

Percentage  of 
catalyst 

Character  of 
product 

Butyro-refrac- 
tion 
(Corrected  to 
40°  C.) 

Melting  point, 
°C. 

Nickel 

1   00 

Hard 

45  7 

49 

Platinum 

0.10 

Hard 

47.8 

46 

Palladium. 

0  06 

Brittle 

45.5 

52 

The  keeping  properties  of  these  hardened  oils  were  found  to  be 
remarkably  good.  Although  prepared  nearly  a  year  and  a  half  pre- 
viously and  having  often  been  exposed  to  damp  air,  yet  they  showed 
no  signs  of  rancidity.  The  free  acidity  (0.70  per  cent  as  oleic  acid) 
did  not  appreciably  change  during  the  period  of  observation. 

Bomer*  is  in  substantial  agreement  with  the  foregoing,  for  he  states 
that  (1)  the  hardened  oils,  as  a  result  of  the  more  or  less  complete 
transformation  of  unsaturated  fatty  acids  (oleic,  linoleic,  linolenic) 
into  stearic  acid,  show  an  increase  in  the  melting  and  solidifying  points 
as  well  as  a  lowering  of  the  refractometer  number  and  iodine  number 
while  the  saponification  number  is  but  little  altered. 

(2)  Judging  by  the  iodine  numbers  of  the  liquid  fatty  acids,  these 
acids  appear  to  be  not  uniformly  transformed  into  stearic  acid,  but 
the  transformation  of  oleic  acid  appears  to  progress  more  slowly  than 
the  less  saturated  linoleic  and  linolenic  acids,  etc.f 

(3)  Among  the  hardened  oils,  the  soft  and  medium-hard  products, 
in  color,  consistency  and  in  part  also  in  odor  and  taste  show  a  greater 
or  less  similarity  to  beef  or  mutton  tallow,  so  that  by  external  appear- 

*  Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1912),  220. 

t  Muller  (Seifen.  Ztg.  (1913),  1376)  examined  a  hydrogenated  fish  or  whale  oil 
known  as  Talgit,  having  an  iodine  number  of  49,  and  found  the  iodine  number  of 
the  liquid  fatty  acids  obtained  from  this  material  to  be  100,  from  which  he  concludes 
that  the  addition  of  hydrogen  occurs  simultaneously  with  both  the  oleic  and  the 
more  unsaturated  acids  and  not  successively  in  such  a  manner  as  to  convert  the 
acids  containing  two  or  more  double  bonds  into  oleic  acid  before  oleic  becomes 
transformed  into  stearic  acid. 


290 


THE  HYDROGENATION  OF  OILS 


ance  one  cannot  distinguish  these  hardened  oils  from  such  animal 
fats;  for  example  medium-hard  peanut  oil  is  so  completely  like  neutral 
lard,  and  hardened  whale  oil  is  so  like  mutton  tallow,  that  one  is  not 
able  to  distinguish  between  these  fats  by  appearance,  consistency, 
odor  or  taste. 

(4)  Not  only  in  their  outward  properties  are  these  hardened  oils 
like  hog  fat  and  mutton  tallow,  but  also  the  usual  analytical  constants 
are  so  similar  that  one  cannot  distinguish  some  samples  of  hardened 
peanut  oils  and  hardened  sesame  oil  from  hog  fat,  nor  whale  oil,  in 
some  cases,  from  mutton  or  beef  tallow.  In  the  latter  case  even  the 
Polenske  numbers  agree  while  in  the  case  of  sesame  oil  they  are  some- 
what lower  than  hog  fat. 


Oil 

Appearance 

Melt- 
ing 
point 

Solidi- 
fying 
point 

Refrac- 
tometer 
at  40° 

Acid 
No.* 

Saponi- 
fication 
No. 

Iodine 
No. 

Peanut  oil  un- 
treated 

Yellow  liquid.  .  .  . 

56.8 

1.1 

191.1 

84.4 

Peanut  oil 
hardened  

White  tallowy  .  .  . 

51.2 

36.5 

50.1 

1.0 

188.7 

47.4 

Sesame  oil 
hardened  

White  tallowy  .  .  . 

62.1 

45.3 

38.  4t 

4.7 

188.9 

25.4 

Cottonseed  oil 
hardened 

Yellowish 
lard  like  

38.5 

25.4 

53.8 

0.6 

195.7 

69.7 

Cocoanut  oil  un- 
treated 

White  soft  

25.6 

20.4 

37.4 

0.3 

255.6 

11.8 

Cocoanut  oil 
hardened  
Whale  oil  hardened.. 

White  lard  like.  .  . 
Yellowish  tallowy 

44.5 
45.4 

27.7 
33.7 

35.9 
49.1 

0.4 
1.1 

254.1 
193.0 

1.0 
46.8 

Milligrams  potassium  hydroxide  for  1  gram  fat. 


t  Determined  at  50°  C. 


Bomer  examined  a  number  of  hydrogenated  oils  and  tabulated  the 
results  of  his  investigations  and  from  these  the  above  condensed  table 
has  been  compiled. 

The  solid  and  liquid  fatty  acids  separated  from  the  hydrogenated 
fat  by  the  method  of  Farnsteiner  showed  the  following  properties: 


Oil 

Solid  fatty  acids 

Liquid  fatty  acids 

M.P. 

Acid  No. 

Refraction  at 
40°  C. 

Iodine 
No. 

Peanut  oil  untreated 

47.6 
42.9 
44.7 
48.3 
44.4 

91.8 
82.9 
88.9 
115.6 
96.0 

Peanut  oil  hardened 

199.7 
199.5 
206.8 
199.5 

Sesame  oil  hardened                

56.4 
45.0 

Cottonseed  oil  hardened  

Whale  oil  hardened 

ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      291 

Samples  of  these  hardened  oils  were  examined  for  cholesterol  and 
phytosterol.  Hardened  peanut  oil  was  found  to  contain  0.4  per  cent, 
sesame  oil  1.9  per  cent,  cottonseed  oil  1.6  per.  cent  and  whale  oil  0.2 
per  cent  of  sterol,  of  which  the  three  first-mentioned  hardened  products 
exhibited  the  typical  crystalline  form  of  phytosterol.  The  melting 
point  of  these  sterols  ranged  from  132°  to  139°  C.,  yielding  acetates 
melting  between  about  126°  and  129°  C.  The  hardened  whale  oil  gave 
a  sterol  melting  at  149.7°  C. 

Bomer  made  a  series  of  fractional  crystallizations  of  hardened  oil 
and  from  a  sample  of  hydrogenated  peanut  oil  obtained  tristearin 
(amounting  to  about  f  per  cent).  Bomer  has  called  attention  to  the 
rather  striking  behavior  of  cocoanut  oil.  He  calculated  from  the 
iodine  number  that  the  natural  oil  contained  13  per  cent  of  oleic  acid 
and  after  hydrogenation  approximately  about  1  per  cent  of  this  acid 
was  present.  As  a  result  of  the  transformation  of  12  per  cent  of  oleic 
acid  into  stearic  acid,  the  melting  point  increased  from  25.6°  to  44.5°  C., 
or  thus  18.9°  C.,  while  the  solidifying  point  advanced  from  20.4°  to 
27.7°  C.,  or  only  7.3°  C. 

.  Bomer  *  has  studied  the  melting  points  of  hydrogenated  oils  and  as 
regards  hydrogenated  peanut  and  sesame  oil  he  notes  that  the  melting 
points  of  the  least  soluble  glycerides  are  very  high,  being  70.6°  C.  and 
71.5°  C.  respectively,  while  the  corresponding  fatty  acids  melted  at 
68.6°  C.  and  68. 5°  C.;  hence  these  glycerides  apparently  consist  of 
tristearin.  The  hydrogenated  cottonseed  oil  examined  yielded  a  mix- 
ture of  glycerides  of  melting  point  61.3°  C.  and  derived  fatty  acids 
melting  at  38°  C. 

A  species  of  hardened  fish  or  whale  oil,  known  as  "Talgit,"  has  been 
examined  by  Mullerf  who  found  the  product  to  have  an  acid  value  of 
12.8,  an  iodine  number  of  49  and  a  titer  (fatty  acids)  of  39.4°  C.  The 
fat  was  saponified  and  pressed  to  obtain  stearic  acid.  It  was  found 
that  the  operation  of  pressing  could  be  carried  out  effectively  to  yield 
a  product  technically  free  from  liquid  fatty  acids;  35  per  cent  of  solid 
fatty  acid  having  a  titer  of  48.7°  C.  was  thus  obtained.  Muller  states 
that  since  mixtures  of  stearic  and  palmitic  acids  possess  a  solidifying 
point  above  53.5°  C.  the  low  titer  of  the  solid  acids  of  Talgit  points  to 
the  presence  of  solid  acids  other  than  stearic  and  palmitic.  DubovitzJ 
thinks  the  low  melting  point  to  be  due  to  the  presence  in  the  original 
fish  or  whale  oil  of  hypogaeic  and  physetoleic  acid  or  similar  acids  with 
possibly  unsaturated  fatty  acids  of  a  still  lower  number  of  carbon  atoms. 

*  Z.  Untersuch.  Nahr.  Genussm.  1914,  153;  J.  S.  C.  I.,  1914,  323. 
t  Seifen.  Ztg.  (1913),  1376. 
t  Ibid.  (1913),  1445. 


292 


THE  HYDROGENATION  OF  OILS 


Leimdorfer*  regards  the  stearin  produced  by  the  hydrogenation 
of  some  oils  to  be  perhaps  an  allotropic  form  of  natural  stearin. 

The  hydrogenation  of  linseed,  peanut  and  sesame  oil,  using  nickel 
oxide  as  a  catalyzer,  according  to  Bedford  and  Erdmann,  affords 
approximately  pure  stearic  glyceride.f 

An  attempt  is  made  by  Grimme  J  to  identify  fish  oils  after  they 
have  been  hardened.  As  stated,  the  ordinary  constants  give  no  clue 
to  the  original  source  of  a  hardened  oil  and  hence  Grimme  resorts  to 
color  reactions.  A  list  of  tests  is  given  for  each  of  the  four  classes  of 
fish  oils:  (1)  Seal  oils;  (2)  Whale  oils;  (3)  Liver  oils;  (4)  Fish  oils; 
and  also  characteristic  tests  for  individual  oils.  These  tests  were  also 
applied  to  two  hardened  oils  of  unknown  origin  and  Grimme  believes 
from  his  results  that  the  color  reactions  are  characteristic  enough  to 
establish  the  presence  of  fish  oils.  Nickel  was  found  in  the  samples, 
Fortini's  test  (as  detailed  below)  giving  the  strongest  coloration. 
Color  reactions  were  applied  to  six  authentic  whale  oils  from  two  dif- 
ferent sources,  and  hardened  to  different  degrees.  These  tests  were 
carried  out  by  dissolving  5  parts  of  the  sample  in  95  parts  of  benzine- 
xylene  (1  : 1)  and  agitating  5  cc.  of  the  solution  with  the  reagent; 
after  5  minutes  and  60  minutes  the  color  was  noted.  Grimme  finds 
the  iodine-sulfuric  acid  reaction  (1  cc.  concentrated  sulfuric  acid  and 
1  drop  tincture  of  iodine)  to  give  a  characteristic  violet-red  color  for 
whale  oil  though  the  intensity  of  coloration  decreases  with  increasing 
hardness.  The  constants  of  the  six  samples  of  hydrogenated  fish  and 
whale  oils  employed  and  the  coloration  produced  by  different  reagents 
are  tabulated  by  Grimme. 


CONSTANTS  OF  HYDROGENATED  FISH  AND  WHALE  OILS 


Sample 

Consistency 

Specific 
gravity 

Melt- 
ing 
point 

Solidi- 
fying 
point 

Index 
of  re- 
fraction 

Acid 
No. 

Acid 
No.  as 
free 
oleic 
acid,  % 

Saponi- 
fication 
No. 

Iodine 
No. 

(Wijs) 

I 

Lard  like  .  . 

0.9256 

°C. 

38.5 

°C. 

32.8 

1.4569 

3.72 

1.91 

188.8 

56.76 

II    

Tallowy  .  .  . 

0.9259 

40.0 

35.2 

1.4548 

8.49 

4.26 

189.8 

49.82 

in  

Tallowy.  .  . 

0.9258 

42.4 

36.4 

1.4543 

5.64 

2.90 

189.6 

41.36 

IV 

Tallowy  .  .  . 

0.9263 

44.8 

39.3 

1  .  4539 

4.39 

2.21 

189.2 

35.71 

v 

Tallowy  .  .  . 

0.9271 

47.2 

41.5 

1.4536 

4.40 

2.25 

188.7 

26.95 

VI     

Tallowy  .  .  . 

0.9271 

48.0 

42.0 

1.4530 

2.18 

1.10 

189.3 

23.18 

*  Ibid.  (1913),  1317. 

t  Jour.  f.  prakt.  Chem.,  1913,  432. 

J  Chem.  Rev.  u.  d.  Fett  und  Harz  Ind.  (1913),  129  and  155. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      293 


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294  THE  HYDROGENATION  OF  OILS 

A  draft  of  the  Codex  alimentarius  Austriacus,  which  has  been  pre- 
pared by  a  board  of  prominent  chemists  and  officials  including  Hefter, 
Wolfbauer,  Fischer,  Hartl  and  Pellischek,*  embraces  the  subject  of 
hydrogenated  oils  and  it  is  stated  that  considered  as  a  food  product 
these  oils  will  require  further  careful  investigation  before  it  is  deter- 
mined with  certainty  just  what  rank  they  will  take  as  edible  products. 
It  is  noted  that  the  fats  now  offered  for  edible  purposes  are  white  to 
yellowish  in  color,  almost  odorless  and  tasteless.  Usually  the  con- 
sistency lies  between  that  of  ordinary  butter  and  hard  tallow.  Now 
and  then  samples  are  found  which  melt  at  about  60°  C.  and  are  as 
brittle  as  carnauba  wax.  These  hard  products,  of  course,  are  not 
intended  by  themselves  to  be  used  for  edible  purposes,  but  are  em- 
ployed to  raise  the  melting  point  of  soft  fats.  Samples  of  hardened 
peanut  and  sesame  oil  with  iodine  numbers  reduced  to  50  or  lower, 
sometimes  down  to  20,  have  been  examined.  Cocoanut  oil  with  an 
iodine  number  of  2  or  even  lower  has  been  met  with.  The  cholesterol 
of  animal  fats  and  the  phytosterol  of  vegetable  oils  are  not  altered  by 
the  hydrogenation  process.  The  hardened  fats,  it  is  stated,  scarcely 
ever  appear  on  the  market  in  their  true  light,  but  usually  are  put  out 
under  some  trade  name  such  as  "  Peanut-oleo,"  "  Sesame-oleo," 
"  Peanut-margarine,"  "  Sesame-margarine,"  "  Crisca,"  and  the  like. 

Hardened  oils  examined  by  Aufrechtf  in  outward  appearances 
resembled  palm  kernel  oil.  They  were  very  hard  and  of  granular 
fracture,  were  either  pure  white  or  yellowish  in  color.  A  distant  odor 
was  perceptible  on  melting  or  heating.  The  taste  recalled  that  of 
tallowy  fats.  The  products  were  readily  soluble  in  the  usual  fat 
solvent  mediums,  but  the  solubility  in  methyl  and  ethyl  alcohol  was 
very  slight.  The  fats  were  easily  saponifiable.  The  content  of  free 
fatty  acid  fluctuated  between  0.51  to  0.83  per  cent.  The  ash  reacted 
alkaline  and  consisted  of  alkali  carbonate  and  traces  of  iron  oxide,  but 
no  nickel  or  other  constituent  could  be  detected.  The  analytical 
results  are  given  in  table  on  the  following  page. 

The  detection  of  traces  of  nickel  by  the  usual  analytical  methods  is 
often  difficult.!  Dimethylglyoxime,  proposed  by  Tchugaeff,  is  a 
reagent  of  great  sensitiveness.  Its  application  has  been  investigated 
by  a  number  of  chemists,  and  among  these  Bianchi  and  Di  Nola§ 
report  that  the  presence  of  copper  and  iron  interferes  with  the  test. 
They  worked  with  an  acid  reagent  and  used  the  following  procedure: 

*  Seifen.  Ztg.  (1913),  1087. 
t  Pharm.  Ztg.  (1912),  876. 

$  Methods  of  determination  are  given  by  Grossmann,  Die  Bestimmungmethoden 
dee  Nickels  und  Kobalts,  Stuttgart,  1913. 
§  Boll.  Chim.  Farm.  (1910),  517. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      295 


To  the  substance  supposed  to  contain  nickel  one  or  two  drops  of 
concentrated  hydrochloric  or  nitric  acid  are  added  and  the  acid  solu- 
tion so  obtained  is  placed  in  a  porcelain  dish,  or  preferably  on  a  strip 
of  filter  paper.  A  few  drops  of  ammonia  are  added,  or  in  case  the 
strip  of  filter  paper  is  used,  this  may  simply  be  exposed  to  the  vapors 
of  ammonia.  The  liquid  is  acidified  with  acetic  acid  and  a  drop  of 
concentrated  alcoholic  solution  of  dimethylgloxime  is  added.  The 
presence  of  nickel  is  shown  by  a  red  coloration  which  grows  more  pro- 
nounced in  the  course  of  time.  This  reaction  is  a  very  simple  one  and 
does  not  require  any  particular  technical  knowledge  for  carrying  out. 


1 

Durotol 
(yellow) 

2 
Durotol 

(white) 

3 
Hydrogen- 
ated  train  oil 

Color  

Yellowish 

White 

White 

Specific  gravity  at  15°  C 

0  9252 

0  9257 

0  9268 

Melting  point,  °C  

46.5 

46.0 

48.0 

Solidification  point,  °C  

43.5 

43.5 

45.5 

Viscosity  at  50°  C  

5.4 

5.4 

5.6 

Acid  No.  (calculated  as  oleic  acid) 

0  51 

0  57 

0  83 

Saponification  No 

162  2 

161  0 

173  5 

Unsaponifiable  matter  (per  cent)  . 

1  92 

2  1 

2  4 

Acetyl  No. 

1  2 

1  2 

0  95 

Iodine  No. 

3  9 

4  2 

7  8 

Hehner  No. 

95  8 

95  8 

96  4 

Reichert-Meissl  No. 

0  38 

0  36 

0  52 

Water  

0.0 

0.0 

0  0 

Ash  . 

0.037 

0.03 

0.05 

Fortini  *  has  simplified  this  reaction  and  uses  an  alkaline  instead  of 
an  acid  reagent  which  apparently  gives  more  satisfactory  results  than 
the  above  procedure.  Fortini  mixes  one-half  gram  of  dimethyl- 
glyoxime,  5  cc.  98  per  cent  alcohol,  and  5  cc.  concentrated  ammonium 
hydroxide  in  the  order  given,  yielding  a  clear,  faintly  yellowish  liquid 
which  in  glass-stoppered  bottles  may  be  kept  for  a  long  time  unchanged. 
The  test  is  carried  out  as  follows: 

The  sample  to  be  examined  is  freed  from  fat  by  extraction  with 
ether  and  to  the  residue  a  drop  of  the  reagent  is  added.  When  nickel 
is  present  there  will  appear  in  a  few  seconds  a  rose-colored  flock  caused 
by  reaction  with  the  nickel  oxide  present  on  the  surface  of  the  metallic 
nickel.  Of  course,  if  nickel  is  present  in  the  form  of  a  soap,  the  fat 
should  be  extracted  with,  for  example,  aqueous  hydrochloric  acid  in 
the  manner  prescribed  by  Knapp  in  the  foregoing.  In  order  to  make 
the  reaction  even  more  sensitive,  the  residue  may  be  heated  for  a  few 
moments  in  an  oxidizing  flame  to  produce  nickel  oxide. 
*  Chem.  Ztg.  (1912),  1461. 


296  THE  HYDROGENATION  OF  OILS 

Kerr*  proposes  the  following  modification  of  the  dimethylglyoxime 
test  for  nickel  in  hy drogenated  oils  and  fats : 

Ten  grams  of  the  fat  to  be  tested  are  heated  on  the  steam  bath  with 
10  cc.  of  hydrochloric  acid  (specific  gravity  1.12),  with  frequent  shaking 
for  2  to  3  hours.  The  fat  is  then  removed  by  filtering  through  a  wet 
filter  paper,  the  filtrate  being  received  in  a  white  porcelain  dish.  The 
filtrate  is  evaporated  to  dryness  on  the  steam  bath,  2  to  3  cc.  of  concen- 
trated nitric  acid  being  added,  after  it  has  been  partly  evaporated,  to 
insure  the  destruction  of  all  organic  matter.  After  the  evaporation  is 
complete  the  residue  is  dissolved  in  a  few  cubic  centimeters  of  distilled 
water  and  a  few  drops  of  a  one  per  cent  solution  of  dimethylglyoxime  in 
alcohol  added.  A  few  drops  of  dilute  ammonia  are  then  added.  The 
presence  of  nickel  is  shown  by  the  appearance  of  the  red  colored  nickel 
dimethylglyoxime.  The  amount  of  nickel  present  may  be  estimated 
by  comparing  the  color  developed  with  that  developed  in  a  standard 
solution  of  a  nickel  salt. 

The  detection  and  determination  of  small  quantities  of  nickel  by 
a-benzildioxime  is  described  by  Atack  f  as  follows : 

An  alcoholic  solution  of  a-benzildioxime  gives  with  nickel  compounds 
a  bulky  red  precipitate  which  is  insoluble  in  water,  alcohol,  acetone, 
10  per  cent  acetic  acid  and  ammonia;  the  precipitate  becomes  reddish 
yellow  on  boiling.  The  reagent  is  much  more  sensitive  than  dimethyl- 
glyoxime, showing  1  part  of  nickel  in  5  million  of  water,  and  the  pre- 
cipitate is  readily  filtered. |  Small  quantities  of  nickel  are  determined 
as  follows:  150  cc.  of  a  hot  saturated  alcoholic  solution  of  the  oxime 
are  added  for  every  0.01  gram  of  nickel,  the  mixture  is  heated  for 
a  few  minutes  on  the  water  bath,  filtered,  the  precipitate  washed 
with  hot  alcohol,  and  dried  at  110°  to  112°C.;  it  has  the  formula 
C28H22N404Ni  and  contains  10.93  per  cent  Ni.  Nickel  may  be  sepa- 
rated from  cobalt  in  ammoniacal  solution.  a-Benzildioxime  is  pre- 
pared by  boiling  10  grams  of  benzil,  dissolved  in  50  cc.  of  methyl 
alcohol,  with  a  concentrated  aqueous  solution  of  8  grams  of  hydroxyl- 
amine  hydrochloride,  for  6  hours,  washing  the  precipitate  with  hot 
water  and  then  with  a  small  quantity  of  ethyl  alcohol,  in  which  it  is 
only  slightly  soluble.  It  may  be  crystallized  from  acetone. 

According  to  Lindt,  nickel  may  be  determined  colorimetrically  by 
means  of  potassium  thio carbonate.  Metals  of  the  hydrogen  sulfide 
group  and  manganese,  cobalt  and  zinc  should  not  be  present.§ 

*  Jour.  Ind.  &  Eng.  Chem.,  1914,  207. 

t  Chem.  Ztg.  (1913),  37,  773. 

J  Compare  Ibbotson,  J.  S.  C.  I.  (1911),  1317. 

§  J.  S.  C.  I.,  1914,  335, 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS      297 

The  hydrogen  value  is  proposed  by  Fokin*  as  a  means  of  deter- 
mining unsaturated  organic  compounds  in  a  manner  similar  to  the 
iodine  values  of  Hubl  and  Wijs. 

The  "  hydrogen  value  "  of  an  organic  compound  is  denned  as  the 
number  of  cubic  centimeters  of  hydrogen  (at  0  degrees  and  760  mm.), 
which  are  absorbed  by  1  gram  of  the  compound.  For  the  test  an 
apparatus  is  devised  consisting  of  a  distillation  flask  (50  to  150  cc.) 
having  a  small  beaker  fused  inside  on  the  bottom,  and  connected  by 
means  of  the  side  tube  to  a  gas  burette  and  a  gasometer  containing 
hydrogen.  In  the  small  beaker  are  placed  about  0.1  gram  of  catalytic 
platinum,  moistened  with  J  cc.  of  water,  and  in  the  flask  the  substance 
to  be  examined  and  20  to  30  cc.  of  alcohol  free  from  dissolved  oxygen. 
Hydrogen  is  admitted  and  the  flask  is  shaken  by  a  shaking  machine 
until  absorption  is  complete.  The  following  hydrogen  values  were 
obtained  by  Fokin,  the  figures  in  parentheses  being  either  the  hydrogen 
values  corresponding  with  Wijs'  iodine  value,  or,  where  indicated,  the 
theoretical  hydrogen  values.  Elaidic  acid,  78.6  to  81.4  (78.8);  oleic 
acid,  86.2  to  87.2  (86.2);  fatty  acids  from  sunflower  oil,  119.6  to  120.8 
(122.9);  fatty  acids  from  linseed  oil,  164.9  to  166.3  (166.0);  castor  oil, 
73.7  (75.5);  croton  oil,  260.9  (theoretical,  258.4);  undecoic  acid, 
115.6  (114.1);  erucic  acid,  39.4  (65.6).  Colophony  does  not  absorb 
hydrogen  under  the  conditions  of  the  test.  The  "  hydrogen  value  " 
of  course  is  not  a  determination  as  yet  of  use  in  the  identification  of 
hardened  oils,  but  is  noted  here  because  of  its  incidental  interest. 

To  detect  the  presence  of  hydrogenated  oil  in  butter  fat  Seiden- 
berg  f  makes  use  of  the  turbidity  point  produced  by  cooling  a  solu- 
tion of  the  fat  in  ether-alcohol.  The  results  obtained  with  three 
samples  of  hydrogenated  oils  differed  considerably,  depending  upon 
the  degree  of  hydrogenation.  The  iodine  numbers  of  these  fats  were 
determined  and  found  to  be  as  follows:  No.  1,  73.4;  No.  2,  34.5; 
and  No.  3,  3.4.  In  No.  1,  the  amount  of  the  saturated  and  less  sol- 
uble glycerides  is  comparatively  small,  so  that  these  latter  do  not 
raise  the  turbidity  point  of  butter  fat  sufficiently  to  serve  for  their 
detection.  The  effect  of  the  saturated  glycerine  produced  by  the 
hydrogenation  is  also  seen  in  a  comparison  of  the  results  between 
hydrogenated  fats  No.  2  and  3.  In  the  case  of  No.  3,  having  an 
iodine  number  of  3.4,  the  addition  of  even  5  per  cent  can  be  detected 
with  certainty,  while  No.  2,  which  has  an  iodine  number  of  34.5,  can 
be  detected  in  quantities  of  10  per  cent  or  above. 

*J.  Russ.  Phys.  Chem.  Soc.,  40  (1908),  700;  J.  Chem.  Soc.  Abstr.,  94  (1908),  II, 
637. 

f  J.  Ind.  Eng.  Chem.,  1918,  617, 


298  THE  HYDROGENATION  OF  OILS 

The  hydrogenation  process  has  been  used  by  Twitchell  for  the 
preparation  of  saturated  fatty  acids  in  connection  with  a  study  of 
the  melting-  and  solidifying-points  of  mixtures  of  fatty  acids  and  the 
use  of  these  points  to  determine  the  composition  of  such  mixtures.* 

Twitchell  prepared  three  fatty  acids,  stearic,  palmitic  and  behenic  acid,  in  a 
fairly  pure  state. 

The  stearic  acid  was  obtained  from  hydrogenated  corn  oil.  The  fatty  acids 
from  this  were  distilled  in  a  current  of  superheated  steam  and  the  last  fraction 
crystallized  a  number  of  times  from  petroleum  ether  and  from  alcohol.  This 
stearic  acid  had  a  solidifying-point  of  69.04°  and  a  melting-point  in  a  capillary 
tube  of  69.30°.  Its  combining  weight,  by  titration  with  alkali,  was  284.  It 
was  not  quite  pure,  as  the  last  crystallization  still  caused  a  slight  increase  of  the 
solidifying-point. 

The  palmitic  acid  was  obtained  from  myrtle  wax,  the  fatty  acids  of  which 
were  distilled  and  then  crystallized  several  times  from  petroleum  ether  and  then 
from  alcohol.  This  had  a  solidifying-point  of  62.14  and  a  melting-point  of  62.44. 
Its  combining  weight  was  255.3. 

The  behenic  acid  was  obtained  from  hydrogenated  menhaden  oil,  the  fatty 
acids  of  which  were  distilled  and  the  last  fractions  crystallized  ten  times  alter- 
nately from  petroleum  ether  and  alcohol.  It  had  a  solidifying-point  of  79.59° 
and  a  melting  point  of  79.99°.  Its  combining  weight  was  340.9. 

It  can  be  assumed,  Twitchell  states,  that  on  hydrogenating  a  fat,  all  those 
unsaturated  acids  containing  18  carbon  atoms  in  the  molecule  are  converted 
into  stearic  acid,  all  those  containing  16  carbon  atoms  into  palmitic  acid  and 
all  those  containing  22  carbon  atoms  into  behenic  acid.  On  comparing  the  mix- 
tures obtained  it  is  seen  that  the  palmitic  acid  has  not  increased  in  the  fatty 
acids  of  the  hydrogenated  product;  therefore,  cottonseed  oil  fatty  acids  contain 
no  unsaturated  acids  with  16  carbon  atoms.  As  the  hydrogenated  oil  fatty  acids 
contain  70.8  per  cent  stearic  acid  plus  2.0  per  cent  of  oleic  acid  the  original  oil 
fatty  acids  would  contain  about  72.8  per  cent  of  unsaturated  acids  with  18 
carbon  atoms,  provided  there  was  no  stearic  acid  originally  present;  at  any  rate, 
it  can  be  concluded  that  all  the  unsaturated  acids  of  cottonseed  oil  have  18 
carbon  atoms  in  the  molecule. 

The  composition  of  the  fatty  acids  of  cottonseed  oil  is  therefore  about  as 
follows: 

Palmitic  acid 25 . 9  per  cent 

Unsaturated  acids  with  18  carbon  atoms 72.8  per  cen" 

The  increase  in  weight  due  to  addition  of  hydrogen,  being  very  small,  has  not 
been  considered  in  the  above  calculations. 

The  hydrogenated  fatty  acids  were  shown  to  contain  25.9  per  cent  of  stearic, 
23.2  per  cent  of  palmitic  acid  and  18.7  per  cent  of  behenic  acid.  The  palmitic 
acid  was  present  in  the  original  oil,  but  the  stearic  and  behenic  acids  have 
been  formed  from  unsaturated  acids  with  18  and  22  carbon  atoms,  respectively. 

The  results  indicate  a  composition  for  menhaden  oil  fatty  acids  about  as 
as  follows: 

*J.  Ind.  Eng.  Chem.,  1914,  564. 


ANALYTICAL   CONSTANTS   OF  HYDROGENATED   OILS     299 

Palmitic  acid 22.7 

Other  solid,  saturated  acids 11.8 

Unsaturated  acids  with  16  carbon  atoms None 

Unsaturated  acids  with  18  carbon  atoms 26.7 

Unsaturated   acids  with  22   carbon  atoms 20 . 2 

Other  Unsaturated  acids 18.6 

100.0 

These  fatty  acids,  therefore,  probably  contain  about  18.6  per  cent  of  another 
Unsaturated  acid  with  some  other  number  of  carbon  atoms,  and  also  11.8  per 
cent  of  another  saturated  acid. 

In  the  course  of  TwitchelPs  previous  work  on  menhaden  oil  as 
above  outlined,  a  fractional  distillation  was  made  of  a  fatty  acid  sep- 
arated from  the  hydrogenated  oil.  There  were  twenty-one  fractions 
in  all.  In  this  distillate  were  found  behenic,  stearic  and  palmitic  acid. 
The  presence  of  arachidic  and  myristic  acid  seemed  probable  but  hav- 
ing neither  of  these  acids  in  the  pure  form,  Twitchell  could  not  at  that 
time  establish  their  presence  in  any  of  the  fractions.  He  therefore 
carried  out  the  following  investigations:  * 

If  any  myristic  acid  were  present  it  would  very  likely  be  found  in  the  first 
fraction.  To  further  concentrate  it,  a  portion  of  this  fraction  was  dissolved  ;n 
alcohol,  partially  precipitated  with  lead  acetate  and  filtered.  The  fatty  acids 
were  separated  from  the  filtrate  and  melted  in  the  proportion  of  20  parts  with 
80  parts  of  myristic  acid: 

The  m.p.  of  this  mixture  was 51 . 60° 

That  of  pure  of  myristic  acid  is 53 . 76° 


The  lowering  of  the  m.p.  was  therefore 2 . 16° 

The  lowering  of  the  m.p.  of  myristic  acid  by  20  per  cent  of  palmitic  acid  is     4.53° 
The  percentage  of  myristic  acid  in  the  fatty  acids  under  examination  is 

therefore  100X(4.53-2.16)/4.53  = 52.3% 

which  clearly  establishes  the  presence  of  myristic  acid  in  the  hydrogenated  oil. 
Arachidic  Acid  in  Hydrogenated  Menhaden  Oil.  Fractions  15  and  16  of  this 
same  distillate  had  an  average  combining  weight  of  308.5  and  were  the  most 
likely  to  contain  arachidic  acid.  They  were  united  and  crystallized  twice  for 
90  per  cent  alcohol  at  15°  C.  The  mean  combining  weight  of  the  crystals  was 
324.  In  previous  work  it  had  been  shown  that  behenic  acid  (molecular 
weight  340)  was  present  in  the  hydrogenated  oil.  It  would  almost  certainly  be 
in  this  faction.  It  remained  to  determine  whether  the  reduction  in  combining 
weight  was  due  to  arachidic  acid. 

*  J.  Ind.  Eng.  Chem.,  1917,  582. 


300  THE  HYDROGENATION  OF  OILS 

20  parts  of  the  crystals  melted  with  80  parts  of  arachidic  acid  has  a 

m.p,  of 72.95 

Arachidic  acid  has  a  m.p.  of 74 . 78 

The  lowering  of  the  m.p.  was  therefore 1 . 83 

The  lowering  of  the  m.p.  of  arachidic  acid  by  20  per  cent  of  behenic 

acid 3.61 

The  percentage  of  arachidic  acid  in  the  crystals  is  therefore  100  X 

(3.62-1.83)/3.61  = 49.3% 

which  establishes  the  presence  of  arachidic  acid  in  the  hydrogenated  oil. 

General  Results.  Having  found  myristic  acid  in  both  the  original  and  the 
hydrogenated  fatty  acids  in  equal  amounts,  it  was  not  produced  by  hydrogena- 
tion.  On  the  other  hand  arachidic  acid  was  found  only  in  the  hydrogenated 
and  not  in  the  original  fatty  acids.  It  was  therefore  produced  by  the  addition 
of  hydrogen  to  an  unsaturated  acid  with  20  atoms  of  carbon. 

The  composition  of  the  menhaden  oil  fatty  acid  described  in  Twitchell's 
paper  of  July,  1914,*  can  now  be  definitely  stated  as  follows: 

Per  cent 

Palmitic  acid 22.7 

Myristic  acid 9.2 

Stearic  acid 1.8 

Unsaturated  acids  with  16  carbon  atoms None 

Unsaturated  acids  with   18  carbon  atoms  =  26. 7  less   1.8  per  cent  stearic 

acid= 24.9 

Unsaturated  acids  with  20  carbon  atoms 22 . 2 

Unsaturated  acids  with  22  carbon  atoms 20 . 2 

From  certain  observations,  Twitchell  concludes  that  the  unsaturated  acid 
with  22  carbon  atoms  found  in  menhaden  oil  and  which,  like  erucic  acid,  is 
converted  by  hydrogenation  into  behenic  acid,  is  nevertheless  not  erucic  acid, 
since  on  fusion  with  caustic  potash  it  is  not  converted  into  arachidic  acid.  It 
is  probably  a  more  unsaturated  acid  which  is  converted  into  stearic  or  palmitic 
acid  by  the  fusion. 

Crossley  f  reports  some  work  carried  out  by  Passmore  on  the  effect 
of  hydrogenation  of  a  number  of  fatty  acids  and  oils  which  is  illustrated 
by  the  figures  contained  in  the  table  on  the  following  page. 

A  specific  reaction  of  marine  animal  oils  and  their  hydrogenation 
products  is  described  by  Tortelli  and  Jaffe.J  The  reaction  depends 
upon  the  fact  that  these  oils  contain  a  chromogenic  compound 
which  remains  unaltered  even  in  the  hydrogenation  process,  and 
towards  which  bromine,  the  reagent  used,  plays  the  part  of  a 
auxochrome,  forming  a  coloring  matter  that  tints  with  a  beautiful 
green  a  chloroform  solution  of  the  oil  tested. 

*J.  Ind.  Eng.  Chem.,  1914,  564. 

fPharm.  Soc.,  Apr.  21,  1914;  Pharm.  J.,  1914,  92,  604,  037  and  676;  J.S.C.I.,  1914, 
1135. 

{Ann.  chim.  applicata,  2,  80-98;    Chem.  Abs.,  1914,  3723;  J.  S.  C.  I.,  1914,  1061. 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED   OILS     301 


% 
Ni 
Used. 

Tempera- 
ture. 

Time 
in 
Hours. 

Iodine  Value 

Melting-point 

Of 
Original 
Sub- 
stance. 

Of 
Product 

Of 
Original 
Substance. 

Of 
Prod- 
uct. 

Ricinoleic  acid  

3 
6 
10 
3 
3 
3 
6 
3 
1 
6 
3 
3 
3 
3 
3 
10 
3 
3 
3 
2 
2 

180° 
100° 
180° 
180° 
240-250° 
180° 
100° 
240-250° 
100° 
100° 
180° 
240-250° 
240-250° 
180° 
240-250° 
180° 
180° 
100° 
175° 
190-200° 
172-185 

2 
4 
1 
1 
2 
2 
3 
i 

H 

2 
If 
If 
If 
3 

li 

H 
1* 
10J 

a 
6 
6 

89.8 
91.8 

120.3 
74.0 
182.1 
176.0 
179.2 
82.9 
82.1 
84.8 
120.0 
123.0 
157.0 
159.5 
181.2 
176.8 
118.2 
119.1 
101.8 
124.5 
92.1 

7.99 
3.69 
5.95 
2.05 
30.00 
7.79 
5.98 
4.08 
9.77 
3.83 
10.30 
27.7 
13.1 
11.1 
9.52 
4.75 
11.2 
24.3 
18.5 
51.5 
22.6 

Liquid 
Liquid 
Liquid 
34° 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 
Liquid 

53° 
72° 
58.5° 
79° 
60.5° 
66° 
65° 
63° 
61° 
63° 
54° 
48.5° 
56° 
57° 
66° 
62.5° 
59° 
56° 
58° 
solid 

Ricinoleic  acid 

Erucic  acid   

Erucic  acid 

Linoleic  acid  

Linoleic  acid.              .  . 

Linoleic  acid 

Oleic  acid  

Oleic  acid 

Oleic  acid  

Whale  oil. 

Whale  oil  

Cod  oil  

Cod  oil 

Linseed  oil  

Linseed  oil. 

Rape  oil  

Rape  oil.  . 

Cottonseed  oil  
Fish  oil  

Almond  oil 

TORTELLI   AND    JAFFE    REACTION 

The  procedure  is  as  follows:  Into  a  graduated  cylinder  (with  foot)  provided 
with  ground-glass  stopper,  and  15  mm.  in  diameter  and  15  cc.  capacity,  are  put 
1  cc.  of  the  oil,  6  cc.  chloroform  and  1  cc.  glacial  acetic  acid.  The  liquid  is 
agitated  until  it  is  homogeneous,  when  40  drops  of  a  10  per  cent  chloroform 
solution  of  bromine  are  added  the  whole  is  again  strongly  agitated  for  a  mo- 
ment and  the  cylinder  placed  upon  a  sheet  of  paper.  If  the  oil  in  question 
belongs  to  the  group  of  marine  animal  oils  it  will  assume  within  a  minute  a 
fugitive  pink  followed  by  a  bright  green  color,  becoming  more  and  more  clear 
and  intense,  and  remaining  so  for  over  an  hour,  after  which  the  color  turns  to 
brown  or  sepia.  The  test  is  sharper  as  the  oil  is  more  purified  or  refined.  Vege- 
table oils,  tested  as  above,  remain  uncolored,  or  at  most  take  on  a  clear  yellow, 
which  does  not  change  within  an  hour,  then  becoming  orange  or  dull  yellow. 
Hemp  oil,  however,  becomes  green  before  addition  of  bromine  and  then  passes 
decidedly  into  yellow.  Oils  of  terrestrial  animals  take  quickly  a  yellowish  color, 
which  in  the  course  of  an  hour  always  darkens  to  brown  or  sepia.  Hydro- 
genated  fats  are  tested  as  follows:  A  larger  cylinder  is  used  (30  mm.  in  diameter 
and  about  25  cc.  in  capacity),  into  which  are  introduced  5  cc.  oc  the  melted  fat, 
10  cc.  chloroform,  and  1  cc.  acetic  acid;  after  agitating  well,  add  2.5  cc.  of  10 


302  THE  HYDROGENATION  OF  OILS 

per  cent  chloroform  solution  of  bromine  and  agitate  again.  There  appears 
almost  immediately  a  fugitive  yellowish  pink,  which  changes  in  a  minute  to  a 
bright  green,  then  quickly  to  an  intense  green,  lasting  over  an  hour.  Many 
tests  were  made  by  Tortelli  and  Jaffe  with  different  oils  and  fats,  and  the  color 
reactions  were  always  positive.  Five  per  cent  of  hydrogenated  fish  oil  in  various 
edible  fats  has  been  detected  by  this  test.* 

The  reliability  of  this  color  reaction  is  questioned  by  Griin  and  Janko.f 
Tests  for  hydrogenated  fish  and  whale  oil  made  according  to  Tortelli  and  Jaffe 
do  not  give  good  results  with  thoroughly  hardened  fats,  but  the  color  reaction 
is  shown  when  incompletely  hydrogenated  products  are  used.J  The  results  ob- 
tained by  the  author  confirm  this  view. 

The  bromine  reaction  of  Tortelli  and  Jaffe  is  stated  by  Davidsohn  § 
to  be  of  little  value  for  the  detection  of  marine  animal  oils,  for  many 
of  such  oils  fail  to  give  a  green  coloration  in  the  test. 

Hydrogenation  products  of  marine  animal  oils  give  an  intense  green  color, 
but  so  also  do  hydrogenized  vegetable  oils,  such  as  linseed  oil  and  soya-bean  oil. 
The  octobromide  test  of  Marcusson  and  Huber  fails  with  marine  animal  oils 
which  have  been  hydrogenated  or  strongly  heated,  but  is  to  be  preferred  to 
Tortelli  and  Jaffe's  test,  because  its  indications  are  trustworthy  when  a  positive 
result  is  obtained. 

Tsujimoto||  advises  that  most  marine  animal  oils  give  the  Tortelli- 
Jaffe  color  reaction  If  especially  when  the  oils  are  fresh.  Old  and 
inferior  samples,  however,  give  no  coloration,  or  the  coloration 
obtained  is  indistinct.  In  some  cases,  the  coloration  is  given  by  old 
oils  after  these  have  been  refined.  The  mixed  fatty  acids  of  marine 
animal  oils  as  well  as  their  distillates  give  the  coloration,  but  the 
unsaponifiable  matters  and  higher  unsaturated  fatty  acids  do  not 
enter  into  the  reaction.  Hydrogenated  fish  oils  give  indistinct  colora- 
tions with  the  test;  vegetable  oils  and  terrestrial  animal  oils  and 
fats  do  not  give  a  reaction. 

Fryer  and  Weston**  observe  that  apart  from  the  question  of  wilful 
sophistication  of  an  oil  or  fat,  a  new  problem  for  the  oil  chemist 
has  been  created  by  the  introduction  of  hydrogenated  oils  in  com- 
merce. Chemical  and  physical  tests  may  here  give  no  indication 
of  the  natural  origin  of  these  substances  and  in  some  cases  it  may 

*Chem.  Ztg.,   1915,   14. 
f  Seifenfabrikant,   1915,  253-255. 
JSeifen.  Zeitung,  1915,  374. 

§Seifen.  Zeit.,  1915,  42,  657  and  678;  Z.  angew.  Chem.,  1915,  28,  Ref.,  560; 
J.  S.  C.  I.,  1916,  186. ; 

||  J.  Chem.  Ind.  Japan,  1915,  18,  1368;    J.  S.  C.  I.,  1916,  262. 

t  J.  S.  C.  I.,  1914,  1061. 

**  Technical  Handbook  of  Oils,  Fats  and  Waxes,  1917,  Vol.  I,  64. 


ANALYTICAL   CONSTANTS  OF  HYDROGENATED  OILS    303 

be  impossible  even  to  distinguish  them  from  natural  products. 
There  are,  however,  certain  differences  in  appearance  and  character 
which  to  the  practised  eye  may  serve  to  subject  them  to  suspicion. 
The  specific  color  reactions  for  cottonseed  and  apparently  for  sesame  oil 
are  of  no  avail  on  account  of  the  destruction  of  the  color-producing 
substances  present  in  these  oils.*  The  presence  of  phytosterol  in 
a  stearine  would  prove  a  vegetable  origin;  and  liver  oils  would  still 
be  recognized  by  the  color  reaction  with  sulphuric  acid.  A  hardened 
maize  oil  might  be  detected  by  the  presence  of  lecithin.  Apart  from 
this  it  would  seem  to  be  next  to  impossible  in  many  cases  to  discover 
with  certainty  the  source  of  an  oil  hardened  by  hydrogenation. 

Pickering  f  considers  the  only  likely  method  for  the  determination 
of  the  origin  of  hardened  oils  is  in  the  separation  of  the  liquid  fatty 
acids,  bromination  of  these  liquid  acids,  and  separation  of  the  bromides. 
The  bromides  from  marine  animal  and  fish  oils  char  on  heating,  while 
the  bromides  from  vegetable  oils  and  fats  give  a  definite  melting-point 
without  any  charring. 

Results  obtained  by  Sandelin  J  on  the  examination  of  hydrogenated 
products  prepared  from  whale  oil  at  a  factory  in  Kaipiais,  Finland, 
and  also  of  hydrogenated  whale  oil,  made  in  Germany  and  offered 
to  a  Finnish  margarine  factory,  were: 


0 

. 

® 

m 

CJ 

r*     W 

^    *O 

a 

a 

"ft 

»  "* 

a 

0 

a 

1 

^2 

•4-.     '3 

o   S 

'o 

I 

I 

s: 

"S 

§ 

•| 

^ 

O    «5 

a^ 

| 

| 

5  c 
«  ^ 

«s  « 

'3  3 

13 

«.? 

1    S 

*    3 

Mil 

| 

"3 

•§  ? 

•s  £ 

a>    ^ 

11 

1 

I  £ 

•§  ? 

•si 

"$   a 

o 

a 

OJ 

£ 

i 

•S 

« 

£ 

^ 

% 

fc 

Original  whale  oil    .      ... 

fluid 

fluid 

64  1 

192  2 

9  50 

144.8 

0.27 

0  69 

287.7 

Artificial  tallow.          

47  5 

38  1 

48  9 

183  7 

9  88 

56.9 

0.25 

0  49 

296.4 

75.5 

1 

Artificial  stearine      

54  3 

47.3 

32.4 

187.7 

7  80 

11.7 

0.14 

0  31 

297.0 

74.1 

4- 

Hydrogenated  whale  oil  (German) 

41.9 

31.9 

48.2 

190.9 

5.30 

57.8 

0.18 

0.50 

282.0 

76.0 

*  Of  the  distinguishing  color  reactions,  the  Halphen  test  is  rendered  negative  by 
the  destruction  of  the  substance  producing  the  color.  The  use  of  pyridine  in  place 
of  amyl  alcohol  and  a  closed  tube  for  the  test  has  been  found  more  sensitive  and 
should,  therefore,  be  employed  in  the  case  of  a  suspected  hardened  cottonseed  oil  to 
detect  traces  of  the  chromogenetic  body.  (Fryer  and  Weston,  Technical  Handbook 
of  Oils,  Fats  and  Waxes,  1917,  Vol.  I,  233.) 

t  Commercial  Analysis  of  Oi's,  Fats  and  Commercial  Products,  Philadelphia,  1917,  64. 

JTeknikern,  1913,  359;  Chem.  Techn.  Rep.,  1914,  38,321;  J.  S.  C.  I.,  1914, 
1097, 


304 


THE  HYDROGENATION  OF  OILS 


THE  ANALYTICAL  CONSTANTS  OF   HARDENED   OILS 
According  to  Lehmann  (Chem.  Ztg.,  1914,  798.) 


Hardened  Oil. 

Melting- 
point  °C. 

Solidify- 
ing-point 
C. 

Differ- 
ence °C. 

Acid 
No.1 

Saponifi- 
cation 
No. 

Iodine 
No.2 

Appearance. 

Peanut  oil  

42.8 

31.6 

11.2 

1.0 

188.2 

59.0 

white,  tallowy 

35.5 

24.4 

11.1 

1.0 

188.5 

62.6 

white,  lardlike 

Peanut  oil         .... 

37.8 

27.0 

10.8 

2.1 

186.9 

59.5 

white,  tallowv 

Peanut  oil     

37.7 

26.8 

10.9 

white,  tallowy 

Sesame  oil  
Sesame  oil  

35.2 
36.9 
35  8 

24.2 
24.4 
24  5 

11.0 
11.5 
11  3 

3.0 
3.1 

185.0 
190.2 

65.6 
64.9 

white,  lardlike 
white,  tallowy 
white,  tallowy 

Cottonseed  oil  .... 
Cottonseed  oil  .... 

30.0 
33.6 

18.2 
21.8 

11.8 
11.8 

0.3 
0.4 

193.7 
192.5 

70.9 
69.0 

yellow,  lardlike 
yellow,  tallowy 

1  Milligrams  of  caustic  potash  per  gram  of  fat. 


2  Hubl  Method. 


The  iodine  values  of  hydrogenated  oils  which  before  hardening  had 
high  iodine  numbers  have  been  determined  by  Kelber  and  Rheinheimer  * 
using  the  methods  of  Gaebel,  Huebl,  and  Wijs  and  concordant  results 
were  obtained  by  all  three  methods  provided  a  sufficiently  long  time 
was  allowed  for  the  action  of  the  iodine  solution. 

In  determining  the  nickel  content  of  hardened  oil,  Lehmann  f 
employs  the  following  procedure: 

Two  hundred  grams  of  the  fat  are  placed  in  a  half  liter  quartz  dish  and  are 
heated  strongly  until  the  fat  inflames.  The  source  of  heat  is  removed  and  the 
fat  is  allowed  to  burn  quietly.  When  the  combustion  is  nearing  an  end,  a 
small  gas  flame  is  placed  under  the  dish  and  the  considerable  masses  of  carbon 
which  are  present  are  burned  away,  while  taking  care  to  avoid  air  drafts.  The 
slight  residue  of  ash  is  evaporated  once  with  nitric  and  once  with  hydrochloric 
acid  and  is  then  dissolved  in  water  and  the  solution  concentrated.  Concentrated 
ammonia  is  added  to  the  hot  solution  to  precipitate  ferric  hydrate,  which  is 
filtered  off.  After  numerous  tests  with  all  recent  methods,  that  of  Tschugaeff 
for  determining  nickel  was  selected.  The  nickel  solution  is  mixed  with  1  cc. 
each  of  concentrated  ammonia  and  a  1  per  cent  alcoholic  glyoxime  solution. 
Dilution  to  50,  100  or  250  cc.  is  made,  according  to  the  intensity  of  color  en- 
gendered by  the  red  precipitate  which  forms.  The  solution  is  shaken  vigorously 
and  compared  colorimetrically  with  standard  solutions  of  known  nickel  content. 
50  cc.  portions  are  used  for  the  colorimetric  determination  and  before  observa- 
tion the  solutions  are  well  agitated.  The  results  obtained  by  this  method 
agreed  with  those  obtained  by  the  gravimetric  method  of  Brunck.t 

The  nickel  content  of  several  samples  of  hardened  oil  is  shown  in  the  following 
table: 

*Arch.  Pharm.,  1917,  417;  J.  S.  C.  I.,  37,  34A;  Chem.  Abs.,  1918,  1004. 

fChem.  Ztg.,  1914,  798. 

t  Zeitsch.  f.  angew.  Chem.,  1907,  1844;  J.  S.  C.  I.,  1907,  643  and  1217. 


ANALYTICAL  CONSTANTS  OF  HYDROGENATED  OILS    305 


ASH  OF  IIA11PKNKD  OIL 


Oil. 

MILLIGRAMS  PER  KILO. 

Total  Ash. 

Iron. 

Nickel. 

Peanut                                                   .            .    . 

2.3 

1.6 
6.1 
4.2 
5.0 
1.1 
1.1 
1.0 
0.07 
0.5 
0.4 

Peanut 

27.5 

40.0 

5.3 
6.3 

Peanut.                                       

Peanut 

Peanut 

Sesame                                           .            

18.5 
23.0 

6.0 

4.2 

Sesame 

Sesame.                           .    .  .          

Cottonseed 

23.5 
30.0 

3.9 
3.5 

Cottonseed. 

Cottonseed.  .                                            ..... 

The  ash  contained  in  addition  very  small  amounts  of  aluminum,  zinc  and  cal- 
cium. 

The  detection  of  nickel  in  fats  is  carried  out  according  to  Schoenfeld  by  ignit- 
ing 5  to  10  g.  of  the  fat  in  a  porcelain  crucible.  The  ash  is  treated  with  1  cc. 
of  concentrated  hydrochloric  acid  and  heated  on  the  water-bath,  then  dissolved 
in  2  to  3  cc.  of  water,  filtered  and  the  filtrate  evaporated  in  a  small  porcelain 
dish.  After  moistening  with  a  few  drops  of  water  a  solution  of  dimethylglyoxime 
is  added  in  the  usual  manner.  Schoenfeld  observed  that  far  more  certain  results 
are  obtained  in  this  manner  than  by  extracting  the  fat  with  hydrochloric  acid, 
evaporating  the  hydrochloric  acid  solution  and  testing  the  residue  for  nickel.* 

PRALL'S  MODIFIED  TEST  FOR  NICKEL  IN  HARDENED  OIL 

The  test  for  nickel  proposed  by  Prall  involving  extraction  of  the 
oil  with  hydrochloric  acid,  was  not  regarded  by  him  as  reliable  under 
all  conditions  and  he  has  found  the  following  procedure  to  be  more 
satisfactory  :f 

One  hundred  to  200  g.  of  the  fat  are  burned,  little  by  little,  in  a  platinum 
dish,  and  the  residue  is  ignited.  The  ash  is  dissolved  in  3  to  5  cc.  acidulated 
water,  containing  5  to  10  drops  hydrochloric  acid.  The  solution  is  heated 
somewhat  to  remove  a  considerable  portion  of  the  excess  of  acid  and  is  then 
rendered  alkaline  with  ammonia.  On  allowing  to  stand  for  one  hour,  iron 
and  aluminum  precipitate  and  are  removed  by  filtration.  The  filtrate  is  evap- 
orated to  dryness  in  a  small  porcelain  dish.  The  residue  is  moistened  with 
ammonia  and  then  a  small  amount  of  an  alcoholic  solution  of  dimethylglyoxime 
is  added.  Even  with  very  small  amounts  of  nickel  (0.1 — 0.01  m.g.  in  100  g.  of 
fat)  a  distinct  red  coloration  is  apparent. 


*Siefen.  Ztg.,   1914,  946. 

tZeitsch.  f.  Unters.  d.  Nahrungs — u.  Genussmittel,  1912,  109. 


306  THE  HYDROGENATION  OF  OILS 

Positive  results  are  attained  only  by  using  at  least  100  g.  of  the  fat.  The 
most  convenient  method  of  burning  off  the  fatty  matter  is  to  heat  the  sample 
to  the  fire  point  and  allow  the  organic  matter  to  quietly  burn  away.  A  blank 
test  may  be  conducted  by  grinding  nickel  sulphate  with  oil  and  adding  1  cc.  or 
0.1  cc.  (corresponding  to  0.0002  g.  or  0.00002  g.,  respectively  of  nickel)  to  100  g. 
of  oil,  which  is  ignited  and  the  residue  tested  as  noted  above.* 

THE  EFFECT  OF  HYDROGEN  ON  OIL  CONTAINING  DISSOLVED  NICKEL 

A  sample  of  cottonseed  oil  which  the  author  hardened  with  about  1  per  cent 
of  reduced  nickel  catalyzer  was  allowed  to  stand  for  two  years  in  contact  with 
the  catalyzer.  The  hardened  fat  was  then  melted  and  the  catalyzer  removed  by 
filtration.  The  filtered  fat  was  distinctly  green  in  color  and  on  analysis  was 
found  to  contain  0.04  per  cent  of  nickel.  A  quantity  of  the  filtered  fat  was 
subjected  to  a  gradual  increase  of  temperature,  while  a  current  of  hydrogen 
was  passed  through  the  liquid  fat.  Portions  removed  at  145°  C.  and  again  at 
160°  C.,  still  had  a  green  tinge.  At  170°  C.,  the  green  color  practically  disap- 
peared and  at  185°  C.  no  green  color  could  be  detected  although  the  oil  was 
apparently  unblackened  by  formation  of  precipitated  nickel. 

The  determination  of  the  hydrogen  number  is  described  by 
Albright  f  and  although  his  investigations  are  concerned  mainly  with 
essential  oils,  much  of  the  data  secured  is  of  interest  in  connection 
with  the  examination  of  fatty  oils.  A  form  of  colloidal  palladium 
was  used  as  a  catalyzer  J  and  a  method  of  preparing  material  of  this 
character  is  given  by  Albright. 

The  apparatus  used  by  Albright,  which  is  shown  in  Figs.  50a  and  506,  is  similar 
in  principle  to  that  devised  in  the  organic  laboratory  of  the  University  of  Gottingen. 

t 

!"-  /k ***• -H 

i 


B 


FIG.  50a. 

Its  fundamental  parts  are  the  camshaft,  carrying  four  eccentrics;  the  shaking  baskets 
A,  attached  to  the  cams  and  suspended  from  pulleys  on  a  supporting  rod;  the  absorp- 
tion flasks  B,  which  are  placed  in  the  wire  baskets;  the  gas  buret  connected  by  means 
of  a  T  tube  both  with  the  source  of  hydrogen  and  with  the  absorption  flask.  Power 
is  supplied  by  a  f-H.P.  motor  belted  to  the  cam-shaft.  When  in  operation,  the  shaft 
has  a  speed  of  about  200  r.p.m.  Hydrogen  is  supplied  from  a  Kipp  generator, 

*Zeitsch.  angew.  Chem.,  Aufsatzteil,  1915,  40. 

t  J.  Am.  Chem.  Soc.,   1914,  2188. 

j  Paal  and  Amberger,  Ber.,  37,  124,  1904.  j 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED   OILS     307 

or  from  a  steel  cylinder  and  is  purified  by  being  passed  through  a  large  wash  bottle 
containing  alkaline-saturated  permanganate  and  is  washed  with  water  at  each 
gas  buret  by  a  separate  wash  bottle. 

Manipulation.  The  manipulation  of  a  reduction  is  as  follows:  The  air  is  first 
displaced  from  the  entire  apparatus  by  passing  through  it  a  current  of  hydrogen, 
after  removing  the  stopper  C,  and  lowering  the  reservoir  D,  so  that  sufficient  water 
remains  to  form  an  air  trap  at  the  lower  bend  of  the  buret.  The  levels  in  both  arms 
of  the  U  tube  are  then  equalized  at  the  zero  mark.  The  three-way  stopcock  E,  is 
then  closed,  the  stopper  C,  which  had  been  replaced  during  the  flushing  of  the  buret 
with  hydrogen,  is  removed,  and  0.02  g.  dry  colloidal  palladium  introduced  while  a 
current  of  hydrogen  is  passing  through.  Then  50  cc.  of  50  per  cent  alcohol  are  added, 
the  stopper  replaced,  the  stopcock  closed,  the  three-way  cock  E  momentarily  opened 
to  the  air  to  equalize  the  pressure  in  the  apparatus  with  that  of  the  atmosphere, 


FIG.  506. 

and  the  flask  shaken  until  no  more  hydrogen  is  absorbed.  In  this  way  the  errors 
due  to  (1)  absorption  of  hydrogen  by  the  catalyzer,  (2)  solubility  of  the  gas  in  the 
solvent,  and  (3)  consumption  of  hydrogen  by  oxygen  dissolved  in  the  solvent,  are 
removed  from  consideration.  The  buret  is  again  filled  to  the  zero  mark  with 
hydrogen  and  the  shaking  flask  tilted  until  the  palladium  solution  has  drained  from 
the  concave  "  substance  table  "  G.  The  substance  under  investigation  is  dropped 
into  this  table  from  an  oil  pipet  (weighing  bottle),  again  preventing  the  entrance 
of  air  by  maintaining  a  current  of  hydrogen  through  the  apparatus.  The  purpose 
of  this  "  substance  table  "  is  to  prevent  contact  between  the  catalyzer  and  substance 
under  examination  until  the  operator  is  ready  to  start  the  experiment.  The  stopper 
C  is  replaced,  the  cock  is  closed  and  the  cock  E  opened  momentarily  to  the  air  again. 
Connection  is  then  made  by  the  same  stopcock  between  the  shaking  flask  and  the 
buret  and  the  machine  is  at  once  set  in  motion.  The  absorption  of  hydrogen  is 
carefully  watched,  maintaining  the  same  water  level  in  each  side  of  the  buret  by 
regulating  the  flow  of  water  from  the  reservoir.  When  the  reaction  is  finished,  a 


308  THE  HYDROGENATION  OF  OILS 

decided  and  abrupt  decrease  in  the  rate  of  absorption  occurs.  On  the  accuracy 
of  the  observation  of  this  point  depends  the  accuracy  of  the  determination.  The 
end  point  may  readily  be  found  otherwise  by  noting  the  buret  reading  at  frequent 
intervals,  e.g.,  every  fifteen  seconds,  and  plotting  volume  against  time  on  coordinate 
paper,  when  the  break  in  the  resulting  curve  will  give  the  desired  result.  This  point 
was  found  by  drawing  a  straight  line  through  the  first  points,  then  connecting  with  a 
smooth  curve  those  points  which  lie  at  the  right.  The  juncture  of  the  straight  line 
representing  the  main  reaction,  with  the  curved  line  representing  absorption  of 
hydrogen  by  secondary  substances,  if  taken  as  the  end  point. 

Hyland  and  Lloyd  *  state  that  owing  to  the  production  of  partially  hydrogen- 
ated  oils,  having  chemical  and  physical  values  practically  identical  with  those  of 
olive  oil,  which  are  being  placed  on  the  market  as  a  substitute  for  olive  oil  for 
use  in  the  worsted  trade,  etc.,  they  have  attempted  to  discover  some  test  by 
means  of  which  these  .oils  could  be  valued.  Some  hydrogenated  oils  have  been 
placed  on  the  market  that  have  an  iodine  value  practically  the  same  as  that  of 
olive  oil,  but  which,  unlike  olive  oil,  gradually  become  tacky  when  exposed  in 
thin  films  to  moist  air,  such  as  oiled  tops,  etc.  A  study  of  the  oxidation  phe- 
nomena of  various  oils  was,  therefore,  carried  out  but  no  conclusive  results  as 
regards  such  hydrogenated  oils  are  reported. 

A  report  on  fats  and  oils  by  Kerr  f  affords  a  study  of  two  methods 
for  the  detection  of  phytosterol  in  mixtures  of  animal  and  vegetable 
fats:  (1)  Bureau  of  Animal  Industry  method  J  and  (2)  the  digitonin 
method  of  Marcusson  and  Schilling.  § 

Three  samples  were  sent  out:  (1)  Lard  containing  5  per  cent  cottonseed  oil 
and  0.25  per  cent  vaseline.  This  amount  of  vaseline  would  effectually  prevent 
accurate  observations  by  the  present  provisional  method.  (2)  Pure  lard,  rancid. 
Rancidity  interferes  decidedly  with  the  present  method.  (3)  Lard  containing 
2.5  per  cent  hydrogenated  cottonseed  oil  and  2.5  per  cent  soya-bean  oil.  Three 
collaborators  were  led  to  correct  conclusions  by  each  method.  The  digitonin 
method  is  more  simple  and  convenient  but  the  reagent  is  expensive  and  difficult 
to  obtain.  The  Bur.  Animal  Industry  method  requires  more  time  and  labor  in 
manipulation  but  does  not  depend  on  an  expensive  reagent.  Both  methods  are 
decidedly  superior  to  the  present  provisional  method  and  are  recommended  for 
adoption  by  the  Association  as  provisional  methods. 

An  investigation  of  the  Bonier  method  for  detecting  tallow  in 
lard  by  Prescher  ||  led  to  the  examination  of  fifty-eight  fats  of  known 
character  by  both  the  Bonier  If  and  the  Polenske  **  methods  in  order 
to  ascertain  their  relative  efficiency  in  detecting  foreign  fats  in  lard. 

*J.  S.  C.  I.,  1915,  62. 

t  J.  Assoc.  Official  Agr.  Chemists,  1,  513-5,  1915. 

JU.  S.  D.  A.  Bur.  Animal  Ind.,  Circ.  212. 

§Chem.  Abs.,  8,  1022. 

||  Z.  Nahr.-Genussm.,  29,  433-7,  1915. 

f  Chem.  Abs.,  8,  1174. 

**Chem.  Abs.,  2,  716. 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED   OILS     309 

In  the  easo  of  25  samples  of  adulterated  lard  only  3,  containing,  respectively, 

10,  20  and  30  per  cent  of  beef  tallow,  could  be  detected  by  the  Polenske  method, 
the  others,  some  containing  as  much  as  15  per  cent  of  beef  tallow,  giving  nega- 
tive tests.     The  Bomer  method  failed  in  only  two  cases,  in  which  5  and  10  per 
cent,  respectively,  of  beef  tallow  were  present.     Eighteen  samples  of  pure  lard 
gave  negative  tests  by  the  Bomer  method,  the  Polenske  procedure  giving  false 
indications  of  adulterations  in  two  cases.     Hydrogenated  vegetable  oils  give  a 
positive  Bomer    test  and  can    be  distinguished  from  beef  tallow  by  the  phyto- 
steryl  acetate   test.     The  Bomer  method   is  to  be   preferred   for  simplicity  and 
accuracy. 

A  smaller  amount  of  phytosterol  acetate  is  obtained  from  oils 
after  hydrogenation  than  before  this  treatment  according  to  Sprink- 
meyer  and  Diedrichs.* 

Hydrogenated  marine  animal  oils  are  indicated  according  to 
Prescher  f  by  the  color  reactions  of  Tortelli  and  Jaffe,J  together  with 
positive  results  in  Kreis  and  Roth's  test  §  for  arachidic  acid  and  the 
cholesteryl  acetate  test. 

The  presence  of  arachidic  acid  and  a  positive  result  in  the  phytosteryl  acetate 
test  indicate  arachis  or  rape-seed  oils.  Sesame  oil  is  detected  by  the  Soltsien 
and  Baudouin  tests.  An  excessively  low  saponification  value  points  to  rape 

011,  while  cocoanut  and  palm-kernel   oils   are  indicated  by  saponification  values 
exceeding  230  and  by  the  Reichert-Meissl  and  Polenske  values.     Hydrogenated 
castor  oil  has  a  high  hydroxyl  value,  while  hydrogenated  cottonseed  oil  may  be 
detected  by   Becchi's   and   Hauchecorne's   tests.     The   ratio   between  the  iodine 
value  and  refractive  index  is  different  in  hydrogenated  fats  from  the  ratio  in 
animal  fats.     Cocoanut  oil  is  distinguished  by  its  very  low  iodine  value.     Bel- 
lier's  reaction  is  only  applicable  to  a  limited  extent  to  the  detection  of  hydro- 
genated vegetable  oils.     The  diinethylglyoxime  test  for  nickel  may  also  be  incon- 
clusive, since  many  freshly-expressed  oils  give  a  red  coloration  in  the  absence 
of  nickel. 

Completely  hydrogenated  fats  have  been  prepared  by  Mannich 
and  Thiele  ||  by  the  aid  of  a  charcoal-palladium  catalyzer  carrying 
2  per  cent  Pd,  in  a  container  surrounded  by  an  asbestos  jacket  and 
maintained  at  100°.  The  catalytic  material  is  subsequently  and 
completely  removed  by  filtration,  yielding  a  product  free  from  all 
contamination,  an  advantage  stated  to  be  not  possessed  by  the 
colloidal  reduction  process.  This  method  can  with  equal  facility 

*Zeitsch.  f.  Unters.  d.  Nahrungs    u.  Genussm.,  1914,  236;    Chem.  Abs.,  1915,  940. 

t  Z.  Unters.  Nahr.  Genussm.,  1915,  30,  357;  Z.  angew.  Chem.,  1916,  29,  Ref.,  165; 
J.  S.  C.  I.,  1916,  548. 

tJ.  S.  C.  I.,  1914,  1061.  ^-uur~ 

§J.  S.  C.  L,  1913,  201. 

||  Ber.  pharm.  Ges.,  26,  36-38,  1916;  Chem.  Abs.,  1916,  2158;  J.  S.  C.  L,  1910. 
648.  See  also  Thiele,  Dissertation,  Gbttingen,  1914. 


310 


THE  HYDROGENATION  OF  OILS 


be  carried  out  in  a  solvent  medium.     The  oils  operated  upon  and 
the  constants  of  the  resulting  fats  are  given  below: 


Oils. 

M.  P. 

I.  No. 

Sapon.  No. 

M.  P.  of  In- 
soluble Fatty 
Acids 
(Hehnei). 

Olive                   

70° 

0  2 

190  9 

71   0° 

Almond 

72° 

0  0 

191   8 

71   0° 

Peanut  

64-64.5° 

0  0 

191  6 

67  0° 

Sesame. 

68  5° 

0  7 

190  6 

69  5° 

Cacao  butter 

63  5-64° 

0  0 

193  9 

65  5° 

Poppy  
Linseed        

70.5 
68° 

0.3 

0  2 

191.3 
189  6 

71.0° 
70  5° 

Tallow 

62° 

0  1 

197  7 

64  0° 

Lard  

64° 

1  0 

196  8 

62  0° 

Cod  liver  

63° 

1  2 

186  2 

59  0° 

A  chloroform  solution  of  the  hydrogenated  cod-liver  oil  gave  no 
coloration  with  sulphuric  acid. 

The  effect  of  hydrogenation  on  cholesterol  and  phytosterol  has 
been  investigated  by  Marcusson  and  Meyerheim,*  with  the  follow- 
ing results. 

Cholesterol  and  phytosterol  were  separated  from  the  unsaponifiable  matter  of 
natural  and  hydrogenated  oils  and  fats  by  the  digitonin  method  of  Windaus.f 
The  amounts  in  natural  fats  ranged  from  0.03  (tallow)  to  0.38  per  cent  (linseed 
oil).  Calculated  on  the  unsaponifiable  matter  the  proportion  ranged  from  33 
to  55  per  cent  in  the  case  of  the  vegetable  oils  examined,  and  from  8  to  14 
per  cent  in  the  case  of  the  animal  fats  (cod-liver  oil  and  tallow).  In  addition 
to  phytosterol  or  cholesterol  other  alcohols  are  present  in  the  unsaponifiable 
matter,  which  either  neutralize  the  optical  laevorotation  (as  in  the  case  of 
cottonseed  oil)  or  even  produce  dextrorotation  (linseed,  cod-liver,  and  especially 
sesame  oil).  The  presence  of  sesamol  affords  a  means  of  detecting  sesame  oil, 
when  no  color  reactions  can  be  obtained.  The  unsaponifiable  matter  left  after 
separation  of  cholesterol  or  phytosterol  was  a  thick  oil  or  semi-solid  mass  con- 
sisting in  the  main  of  unsaturated  dextrorotatory  alcohols  (laevorotatory  in  the 
case  of  ox  tallow)  and  small  quantities  of  hydrocarbons.  Only  in  the  unsapon- 
ifiable matter  of  dark  cod-liver  oil  were  considerable  amounts  of  hydrocarbons 
found.  The  dextrorotatory  power  of  the  unsaponifiable  matter  of  sesame  oil 
was  greatly  increased  by  the  removal  of  the  phytosterol.  The  iodine  value 
(Htibl- Waller)  of  the  residual  unsaponifiable  matter  ranged  from  56  to  78.  As 
a  rule  hydrogenated  fats  contained  less  cholesterol  or  phytosterol  than  the  cor- 
responding natural  fats,  and  the  proportion  decreased  with  the  degree  of  hydro- 

*Mitt.  k.  Materialpriif.,  1916,  33,  221-225;  J.  S.  C.  I.,  1916,  549;  Seifen.  Ztg., 
1916,  168.  See  also  Willstatter  and  Meyer.  Ber.  41,  2199;  Diels  and  Abderhalden, 
Ber.  39,  884  and  Moreschi,  Rend.  soc.  chim.  ital.  1914  (2)  5,  236. 

fJ.  S.  C.  I.,  1915,   1152. 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED   OILS     311 


genation.     For  example,   the  following  results  were  obtained  in  the  progressive 
hydrogenation  of  a  marine  animal  oil: 


Iodine  Value. 

Solidif.  Pt. 

Cholesterol. 

Original  marine  animal  oil 

114 

Deg.  C. 

Per  Cent. 
0   13 

Talgol                                         

67 

31 

0.10 

Talgol  extra 

36 

38 

0.07 

Candelite                    

20 

42 

0.05 

Candelite  extra                                     .... 

13 

45 

0.02 

The  unsaponifiable  matter  of  hydrogenated  fats  after  removal  of  the  chole- 
sterol or  phytosterol  was  a  yellow  semi-solid  mass,  from  which,  in  the  case  of 
talgol,  and  candelite,  a  saturated  alcohol,  M.P.  59.3°  to  59.8°  C.  could  be  ex- 
tracted with  petroleum  spirit.  It  had  a  refractive  index  of  1.4268  at  100°  C. 
and  appeared  to  be  octodecyl  alcohol.  Transformation  products  of  cholesterol 
were  not  obtained  from  talgol  or  candelite,  but  derivatives  of  phytosterol  could 
be  separated  from  hydrogenated  vegetable  oils.  For  example,  repeated  recrys- 
tallization  of  the  unsaponifiable  matter  of  hydrogenated  linseed  oil  from  96 
per  cent  alcohol  yielded  an  alcohol  (M.P.  75°  C.)  which  did  not  give  the  char- 
acteristic phytosterol  reactions. 

Hydrogenated  marine  animal  oils  may  be  detected  according  to 
Marcusson  and  Huber  *  by  an  examination  of  the  unsaponifiable 
matter  for  the  presence  of  octodecyl  alcohol,  M.P.  60°. 

Tsujimoto  |  has  prepared  and  examined  hydrogenated  chrysalis 
oil.  He  has  found  raw  chrysalis  oil  to  be  unsuitable  for  the  pur- 
pose of  hydrogenation,  as  its  nitrogenous  and  other  impurities 
largely  affect  the  activity  of  the  catalyzer.  The  refining  of  chrysalis 
oil  is  by  no  means  easy;  but  a  method  proposed  by  Tsujimoto, 
which  essentially  consists  in  heating  the  oil  with  5  to  10  per  cent 
by  volume  of  dilute  sulphuric  acid  (sp.  gr.  1.39)  followed  by  treat- 
ment with  Kambara  earth,  gives  an  excellent  result.  The  refined 
oil  hardened  by  nickel  catalyzer  is  a  white  fat  which  may  be  used 
as  a  raw  material  for  soap  making. 

The  composition  of  chrysalis  oil  has  been  as  yet  little  investigated.  The 
results  of  experiments  previously  published  by  Tsujimoto  appear  to  be  the 
only  report  on  this  subject.  He  has  noted  that  the  fatty  acids  of  chrysalis  oil 
consist  of  about  25  per  cent  saturated  and  75  per  cent  unsaturated  acids  (iodine 
value  178.73).  Among  the  saturated  acids,  palmitic  acid  was  identified;  stearic 
acid  is  probably  not  present.  The  unsaturated  acids  consist  of  oleic,  linolenic 
and  isolinolenic  acids;  besides  them,  some  isomers  of  linolic  acid  are  present 
in  a  larger  quantity. 

*  Mitt.  klg.  Material priifungsamt,  34,  54. 
tJ,  Ind.  Eng.  Chem.,  1916,  802. 


312  THE  HYDROGENATION  OF  OILS 

If  the  conclusions  reached  in  the  above-mentioned  investigation  be  correct, 
the  final  product  of  the  hydrogenation  of  these  unsaturated  acids  must  be 
stearic  acid.  Tsujimoto  considered  that  a  study  of  the  product  was  important 
from  the  point  of  view  of  utilizing  the  hardened  chrysalis  oil  for  technical  pur- 
poses and  accordingly  made  certain  experiments  which  are  described  below. 


HYDROGENATION  OF  THE  UNSATURATED   (LIQUID)  FATTY  ACIDS  OF  CHRYSALIS  OIL 

Fifty  grams  of  chrysalis  oil  were  saponified  in  a  flask  with  38  cc.  of  50  per  cent 
aqueous  solution  of  KOH  and  113  cc.  of  96  per  cent  alcohol,  by  warming  on  a 
water-bath;  the  excess  of  alkali  was  neutralized  with  acetic  acid  and  500  cc.  of 
7  per  cent  aqueous  lead  acetate  solution  was  stirred  into  it.  The  resulting  lead 
soap  was  twice  washed  with  500  cc.  of  hot  water  and  treated  with  500  cc.  of 
ether  at  10°  C.  and  then  filtered.  (Tortelli  and  Ruggeri's  method.)  The  fil- 
trate was  then  treated  with  dilute  HC1,  in  order  to  decompose  the  lead  soap, 
and  was  well  washed  with  water:  250  cc.  of  the  ethereal  solution  of  the  free 
unsaturated  acids  thus  obtained,  which  contains  about  20  g.  of  acids  of  iodine 
value  176.17,  were  transferred  into  a  strong  glass  bottle;  0.5  g.  of  Loew's  plat- 
inum black  was  added.  The  bottle  was  then  connected  to  a  hydrogen  holder. 
On  expelling  the  air  from  the  bottle  by  hydrogen,  it  was  strongly  shaken  by 
means  of  a  mechanical  contrivance.  After  3£  hours  shaking,  a  loss  of  about 
2900  cc.  of  hydrogen  was  observed  on  the  holder.  Here  the  hydrogenation  was 
stopped  for  a  time.  On  evaporating  off  the  ether,  a  residue  amounting  to 
17.52  g.  was  obtained.  It  was  a  brown-yellow  crystalline  mass  which,  when 
melted,  formed  a  brown-red  liquid;  it  melted  at  56.2°  C.,  having  the  neutraliza- 
tion value  188.92  and  iodine  value  45.91.  The  hydrogenation  was  apparently 
incomplete;  but  before  continuing  the  operation,  it  was  found  better  to  remove 
the  unsaponifiable  and  coloring  matter  from  the  product.  Eleven  grams  of  the  above 
product  were  saponified  with  50  cc.  of  8  per  cent  alcoholic  solution  of  NaOH; 
then  5  g.  of  NaHCOs  and  about  50  g.  of  pure  sand  were  thoroughly  mixed  with  it. 
The  mass  was  dried,  powdered  and  exhausted  in  a  Soxhlet  extractor  with  petro- 
leum ether.  The  crude  unsaponifiable  matter  thus  extracted  was  2.22  per  cent 
The  soap  in  the  extractor  was  dissolved  in  hot  water  and  decomposed  with  dilute 
HC1  and  then  taken  up  with  ether.  The  ethereal  solution  of  the  fatty  acids 
which  appeared  brownish  yellow,  was  decolorized  with  animal  charcoal,  and  made 
up  to  250  cc.  by  adding  ether;  then  adding  0.3  g.  of  the  platinum  black,  it  was 
hydrogenized  for  two  hours  in  the  same  way  as  before  (the  reading  of  the  volume 
of  hydrogen  was  omitted.)  On  evaporating  off  the  ether,  8.3  g.  of  the  hydro- 
genated  acids  were  obtained.  The  white  crystalline  mass  had  a  melting-rrint 
of  68  to  68.5°  C.,  neutralization  value  195.19  and  iodine  value  0.  This  product 
is,  therefore,  a  saturated  compound,  which  in  its  M.P.  and  neutralization  value 
nearly  coincides  with  stearic  acid  (M.P.  69.3°  C.,  neutralization  value  197.5, 
molecular  weight  284).  A  mixture  of  the  product  with  about  an  equal  quan- 
tity of  pure  stearic  acid  melted  at  68  to  68.3°  C.  In  order  to  perform  the 
fractional  crystallization  of  the  acids,  5  g.  of  the  hydrogenated  product  were 
dissolved  in  100  cc.  of  90  per  cent  alcohol  and  separated  into  three  portions 
successively  as  follows:  (1)  4.27  g.;  white  lamina?  with  pearly  luster;  M.P. 
69.5  to  70°  C.;  neutralization  value  197.82;  mean  mol.  wt.  283.59.  A  mixture 
with  pure  stearic  acid  melted  at  69.5°  to  69.7°  C.  (2)  0.21  g.;  M.P.  68°  C.; 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED   OILS     313 

neutralization  value  197.20.     (3)  Residue  left  on  evaporating  the  mother  liquor, 
0.41  g.;   a  little  colored  solid;    M.P.  50°  C.;   neutralization  value  177.42. 

The  low  melting-pomt  and  neutralization  value  are  probably  due  to  the  accumu- 
lation of  the  impurities  in  this  part  and  also  to  the  esterification  of  the  acids  on 
evaporating  off  alcohol.  The  result  of  the  elementary  analysis  of  (1)  was  as  follows: 
0.1245  gave  0.3487  CO2  and  0.1439  H2O;  C  =  76.39;  H  =  12.84.  C]8H36O2  required 
C  =  76.06;  H  =  12.68.  Therefore  the  substance  is  stearic  acid.  From  the 
above,  it  was  concluded  that  the  hydrogenated  product  of  the  unsaturated  fatty 
acids  of  chrysalis  oil  consists  mainly  of  stearic  acid. 

By  the  hydrogenation  of  spinacene,  a  hydrocarbon  from  certain  fish 
liver  oils,  with  platinum  black  as  catalyst,  Chapman  *  found  the 
iodine  value  was  reduced  to  18,  and  a  hydrocarbon,  CsoH^,  boiling 
at  274°  to  275°  C.  (18  mm.)  was  obtained.  This  was  a  colorless,  odorless 
oil  not  solidifying  at  -20°  C.,  and  having  a  sp.gr.  of  0.8172  at  20°/ 
20°  C.  The  unsaturated  hydrocarbon  squalene  separated  by  Tsujimoto 
closely  resembles  spinacene. 

The  glycerol  content  of  hardened  fats  was  determined  by  Normann 
and  Hugel  |  using  several  of  the  published  methods  and  the  results 
obtained  compared  with  those  calculated  from  the  ester  values. 
The  results  obtained  by  the  bichromate  method  agreed  very  well 
with  the  calculated  values.  Wilstatter's  method  J  gave  satisfactory 
results,  but  the  results  obtained  by  the  acetin  method  were  1J 
per  cent  lower  than  the  calculated  values. 

In  the  identification  of  hardened  marine  oils  and  rape  oil,  Nor- 
mann and  Hugel  §  supplement  the  usual  melting-point  test  for 
arachidic  acid  by  the  determination  of  the  saponification  value  of 
the  fatty  acids,  using  an  excess  of  alkali  and  titrating  back  the  excess. 
A  direct  determination  with  N/10  alkali  is  uncertain. 

The  behavior  of .  the  hydroxyl  group  of  the  hydroxylated  fatty 
acids  on  catalytic  hydrogenation  by  means  of  nickel  has  been  studied 
by  Jurgens  and  Meigen  ||.  Nickel  catalyzer  reduces  castor  oil 
below  200°  practically  only  at  the  double  bond  of  the  ricinolic  acid 
radical,  while  above  200°  its  hydroxyl  group  is  also  reduced.  Rici- 
nolic acid  itself  is  little  affected  at  the  lower  temperature  but  its 
hydroxyl  group  is  reduced  at  the  higher  temperature.  Nickel  oxide 
catalyzer  reduces  the  hydroxyl  group  more  rapidly  than  the  double 

*Chem.  Soc.  Trans.,  1917,  56. 

tChem.  Umschau,  1916,  23,  45-47.  Z.  angew.  Chem.,  1916,  29,  Ref.,  371;  J.S.C.I., 
1916,  932. 

*  J.  S.  C.  I.,  1912,  997. 

§Chem.  Umschau,  23,  131-3,  1916;  J.  S.  C.  I.,  1917,  658;  Chem.  Abs.,  1917, 
2736;  Z.  angew.  Chem.,  1917,  30,  Ref.,  108. 

||  Chem.  Umschau,  23,  99-102,  116-20,  1916;  Z.  angew.  Chem.,  30,  II,  34,  1917; 
J.  S.  C.  I.,  36,  657;  Chem.  Abs.,  1917,  2736. 


314  THE  HYDROGENATION  OF  OILS 

bond.  With  2  per  cent  nickel  catalyzer  under  high  pressure  the 
hydroxyl  group  reduction  is  slower  than  at  atmospheric  pressure 
because  the  increased  tension  of  the  steam  from  the  hydroxyl  group 
tends  to  prevent  further  decomposition  of  this  group. 

Svendsen  *  reports  on  the  chemical  composition  of  hardened  whale 
oil.  A  sample  of  hardened  whale  oil  had  acid  value  1.5,  saponifi- 
cation  value  195.7,  iodine  number  59.8,  refractometer  reading  at 
40°  C.,  50;  it  yielded  no  insoluble  bromide.  The  fatty  acids  con- 
sisted of  10.8  per  cent  of  myristic  acid,  17.9  per  cent  of  palmitic 
acid,  10.6  per  cent  of  Bull's  Ci6-acid  f  10.8  per  cent  of  stearic  acid, 
27.7  per  cent  of  oleic  acid,  3.4  per  cent  of  arachidic  acid,  8  per  cent 
of  a  solid  acid,  C22Hs6O2,  2.5  per  cent  of  behenic  acid,  and  8.8  per 
cent  of  an  acid,  C22H4o02. 

Bosshard  and  Fischli  |  give  the  following  method  for  the  deter- 
mination of  hydrogen  in  gaseous  mixtures  by  catalytic  absorption: 

The  absorption  of  hydrogen  by  sodium  oleate  solution  in  presence  of  a  reduced 
nickel  catalyst  is  utilized  for  the  quantitative  determination  of  this  gas  in 
mixtures.  The  catalyst  must  either  be  used  immediately  after  its  preparation 
by  the  reduction  of  nickel  oxide  at  340°  C.,  or  it  must  be  preserved  in  sealed 
glass  tubes  in  3-g.  quantities  in  an  atmosphere  of  hydrogen.  Absorption  is 
effected  in  a  Hempel  pipette  or  in  a  spherical  pipette  with  a  mercury  seal. 
The  gaseous  mixture  is  freed  from  carbon  dioxide,  carbon  monoxide,  oxygen, 
etc.,  by  the  usual  methods,  and  15  to  20  cc.  of  the  residue  is  introduced  into 
the  pipette  charged  with  concentrated  aqueous  sodium  oleate  solution  con- 
taining 3  per  cent  of  the  catalyst  in  suspension;  the  whole  of  the  hydrogen  will 
be  absorbed  after  ten  minutes  shaking.  The  foam  which  is  produced  may  be 
destroyed  by  allowing  a  small  quantity  of  alcohol  to  enter  the  pipette,  but  as 
this  retards  the  rate  of  absorption  it  is  recommended  that  two  pipettes  be  em- 
ployed; when  absorption  is  complete  the  gas  and  foam  are  transferred  to  the 
second  pipette  before  adding  alcohol,  so  that  the  solution  in  the  first  pipette 
may  retain  its  absorbing  capacity  for  a  number  of  operations.  Nitrogen  and 
methane  do  not  interfere.  The  latter  is  determined  by  explosion.  Comparative 
tests  show  the  method  to  be  highly  accurate. 

Anderson  and  Katz  §  do  not  agree  with  the  conclusions  of  Boss- 
hard  and  Fischli.  Commenting  on  the  difficulties  of  handling  the 
reagents,  Anderson  and  Katz  found  that  the  reagent  finally  in  the 
absorption  pipette  without  access  of  air,  samples  of  hydrogen  were 
placed  in  contact  with  it,  but  with  practically  no  absorption.  Many 
attempts  were  made  to  obtain  an  active  reagent,  using  metallic 

*Tidskrift  Kemi,  Farm.,  og  Terapi,  1916,  20,  285-292;  Z.  angew.  Chem.,  1917, 
30;  J.  S.  C.  I.,  1917,  603. 

f  Ci6He0O2,  discovered  by  Bull.,  Ber.,  1906,  3574,  but  not  named  by  him.  Chem. 
Abs.,  i,  305,  Named  palmitoleic  acid  by  Lewkowitsch,  J.  S.  C.  I.,  1906,  1158. 

t  Z.  angew.  Chem.,  1915,  28,  365-366;    Chem.  Abs.,  1916,  26. 

§J.  Ind.  Eng.  Chem.,  1918,  24. 


ANALYTICAL   CONSTANTS   OF  HYDROGENATED  OILS     315 

nickel  prepared  from  nickel  oxide  of  various  degrees  of  fineness 
down  to  200  mesh,  but  with  no  success.  A  temperature  of  80°  C, 
was  maintained  in  the  reagent  in  one  case,  but  to  no  advantage. 
It  was  noticed,  however,  that  the  solutions  of  sodium  oleate  to  which 
nickel  had  been  added  hardened  much  more  quickly  than  those  of 
the  same  concentration  that  contained  no  nickel.  It  was  assumed 
that  this  was  due  to  the  "  hardening  "  of  the  solution  by  the  hydro- 
gen absorbed  by  the  nickel.  Accordingly,  the  preparation  of  nickel 
was  modified  by  substituting  a  current  of  nitrogen  for  the  hydrogen 
at  the  point  when  the  reduction  of  the  nickel  oxide  had  been  com- 
pleted, continuing  the  heating  of  the  material  for  a  short  time  to 
drive  off  occluded  hydrogen.  The  nickel  was  finally  cooled  in  nitro- 
gen and  stored  in  an  atmosphere  of  this  gas.  When  this  material 
was  employed  as  a  catalyst,  the  sodium  oleate  showed  no  ten- 
dency to  harden  sooner  than  it  would  have  done  in  the  absence  of 
nickel,  entirely  in  accordance  with  the  suggested  explanation,  but 
the  reagent  thus  obtained  did  not  absorb  hydrogen  from  gas  mix- 
tures placed  in  contact  ,with  it. 

At  this  juncture,  the  attempt  to  ascertain  the  conditions  under 
which  complete  absorption  of  hydrogen  by  sodium  oleate  in  solu- 
tion might  be  obtained  was  abandoned,  because  of  certain  objec- 
tions inherent  in  the  method  which  would  make  it  of  little  value 
even  when  standardized  and  found  capable  of  giving  satisfactory 
results.  Among  these  objections  might  be  mentioned  the  following: 

1.  The  time  and  effort  required  for  the  preparation  of  the  catalyst 
is  considerable,  and  the  necessity  of  keeping  it  out  of  contact  with 
air  adds  to  the  difficulty  of  its  use. 

2.  The  reagent  foams  badly  and  this  renders  the  absorption  process 
itself  a  lengthy  and  tedious  operation. 

3.  The   rapidity  with   which  even   moderately   dilute   solutions   of 
sodium  oleate  solidify  renders  it  necessary  to  prepare  fresh  solutions 
frequently.     Also,  old  solutions  must  be  discarded  before  they  solid- 
ify in  the  pipette,  otherwise  they  can  be  removed  only  with  difficulty. 

The  hydrogenation  process  is  used  by  Biazzo  and  Vigdorcik  * 
as  a  means  of  determining  colza  or  rape  oil  in  olive  oil.  The  pro- 
cedure is  based  on  the  transformation  of  erucic  into  behenic  acid, 
using  palladium  as  catalyzer.  Behenic  acid  is  characterized  by 
slight  solubility  in  90  per  cent  alcohol,  by  high  melting-point  (84°) 
and  by  its  quantitative  yield  from  erucic  acid.  Recently  very  cheap 
and  powerful  catalytic  palladium  has  been  prepared  by  Mannich 

*Ann.  Chim.  applicata,  6,  185-95,  1916;  J.  S.  C.  I.,  1917,  90;  Chem.  Abs.,  1917, 
713. 


316  THE  HYDROGENATION  OF  OILS 

and  Thiele  *  by  depositing  reduced  palladium  upon  ignited  animal 
charcoal,  giving  a  catalyzer  that  will  saturate  fatty  substances 
completely,  using  1  part  palladium  to  15,000  parts  oil. 

Biazzo  and  Vigdorcik's  method  is  as  follows:  Saponify  20  g.  of  the  oil  and 
extract  fatty  acids  with  ether  and  sulphuric  acid.  Dry  the  ether  extract  with 
calcium  chloride,  distill  off  the  solvent  and  remove  the  last  traces  from  the 
residue  by  placing  in  hot  oven  for  fifteen  minutes  and  blowing  a  current  of  air 
over  it  from  time  to  time.  Dissolve  the  acids  obtained  in  180  cc.  anhydrous 
acetone,  warm  on  the  water-bath  to  incipient  boiling,  add  20  cc.  N  caustic  potash 
and  cool  to  15°.  Collect  the  precipitated  fatty  acids  by  use  of  the  pump,  wash 
with  4  portions  of  10  cc.  cold  acetone,  finally  dissolve  in  water  and  extract  from 
the  solution  the  solid  fatty  acids  with  hydrochloric  acid  and  100  cc.  ether. 
Wash  the  ethereal  extract  twice,  each  time  with  100  cc.  water  and  then  shake 
for  five  minutes  with  15  cc.  30  per  cent  aqueous  solution  of  lead  acetate,  sub- 
sequently removing  the  subnatant  aqueous  layer.  Filter  the  precipitate  "  A  " 
of  lead  soaps  from  the  ethereal  solution  "B,"  first  allowing  the  liquid,  if  neces- 
sary, to  stand  on  a  bath  at  23°  to  25°  for  one-half  hour.  Examine  the  precip- 
itate "A"  for  arachidic  and  lignoceric  acids,  i.e.,  for  arachid  oil.f  Free  solution 
"  B  "  from  lead  by  use  of  hydrochloric  acid  and  wash  till  the  mineral  acid  is 
completely  removed.  Hydrogenate  by  palladium  catalyzer  till  hydrogen  is  no 
longer  absorbed,  filter  and  evaporate  the  solvent.  Treat  the  residue  by  frac- 
tional crystallization  as  in  the  method  of  separating  araehidic  and  lignoceric  acids,  t 
If  the  final  crystallization  gives  a  substance  with  melting-point  above  71°,  the  oil 
under  examination  contains  a  cruciferous  oil.  Positive  indications  are  furnished  by 
a  melting-point  between  76°  to  79.°  The  sensitiveness  of  the  method  depends 
upon  the  care  employed  in  preparing  the  palladium  catalyzer,  and  in  collecting 
and  washing  the  acid  potassium  soaps,  insoluble  in  acetone,  at  15°. 

A  procedure  by  Kelber  §  relates  to  the  removal  of  halogen  from 
organic  halogen  derivatives  by  catalytic  hydrogenation.  Kelber  notes 
that  palladium  has  been  used  for  the  displacement  of  halogens  from 
organic  compounds,  and  it  has  been  found  that  the  reaction  in  pres- 
ence of  palladinized  calcium  carbonate  proceeds  so  completely  that  the 
hydrogenation  process  may  be  used  as  a  quantitative  method  for  the 
determination  of  halogens. 

Equally  satisfactory  results  may  be  obtained  with  nickel  catalysts  and  in  this 
case  it  is  not  necessary  to  recover  the  catalyst.  A  special  shaking  tube  has  been 
designed  for  the  use  of  this  method  for  analytical  purposes.  This  vessel  is  easily 
filled  with  the  catalyst  and  the  halogen  derivative  can  be  added  subsequently; 
any  contact  of  the  liquid  and  catalyst  with  rubber  connections  is  avoided  and 
the  product  of  the  reaction  can  be  quantitatively  removed.  The  catalyst  is 
prepared  by  heating  basic  nickel  carbonate  in  a  current  of  hydrogen  at  310°  to 
320°  C.,  cooling,  and  passing  a  current  of  carbon  dioxide  over  the  material. 
The  catalyst  may  be  kept  for  a  long  time  in  closed  vessels.  For  each  deter- 

*Chem.  Abs.,  10,  2158. 

f  Chem.  Abs.,  1917,  712. 

J  J.  S.  C.  I.,  1913,  201. 

§Ber.,  1917,  305;    J.  S.  C.  I.,  1917,  568  and  1916,  382  and  1130. 


ANALYTICAL   CONSTANTS   OF   HYDROGENATED  OILS     317 

mination,  3  g.  of  the  catalyst  is  placed  in  the  reaction  tube,  shaken  with  water 
or  dilute  alcohol  and  0.5  to  1.0  g.  of  alkali  hydroxide  in  presence  of  hydrogen 
until  no  more  of  the  gas  is  absorbed,  and  the  substance  to  be  analyzed  is  then 
sucked  in  and  the  funnel  rinsed.  Shaking  is  continued  for  some  time  after  the 
reaction  with  the  hydrogen  is  complete,  the  nickel  is  filtered  off  and  washed,  and 
the  halogen  in  the  liquid  determined  either  gravimetrically  or  by  titration.  In 
the  case  of  amino  compounds  or  compounds  which  form  precipitates  with  silver, 
the  organic  by-products  should  be  shaken  out  with  ether  before  making  the 
halogen  determination. 

Commenting  on  an  article  by  Moore,  Richter  and  Van  Arsdel, 
Lowenstein  *  expresses  surprise  that  the  writers  of  this  article  made 
the  statement  that  the  amount  of  hydrogenation  which  is  required 
to  render  the  oil  just  incapable  of  responding  to  the  Halphen  test 
has  not  to  their  knowledge  been  investigated,  in  view  of  Lowen- 
stein's  Patent  No.  1,187,999.  In  reply  to  this,  Moore,  Richter  and 
Van  Ardsale  comment  as  follows: 

In  reply  to  Dr.  Arthur  Lowenstein's  criticism  of  a  section  in  our  article  on 
"  The  Incomplete  Hydrogenation  of  Cottonseed  Oil,"  we  wish  to  state  that 
U.  S.  Patent  No.  1,187,999  was  familiar  to  us  at  the  time  the  section  in  ques- 
tion was  written:  neither  at  that  time  nor  at  the  present  time,  however,  could 
we  regard  the  disclosures  of  the,  patent  as  constituting  anticipation  of  our  work. 

The  fundamental  statement  of  the  patent,  as  quoted  above  by  Dr.  Lowen- 
stein, is  as  follows:  "...  the  hydrogenation  process  is  continued  until  a  sample 
of  the  oil  fails  to  respond  to  the  Halphen  reaction  and  the  desired  degree  of 
crystallization  takes  place  when  the  oil  is  .chilled."  There  is  no  warrant  for 
assuming  from  the  language  of  the  patent  that  when  the  Halphen  test  is  just 
destroyed  the  proper  amount  of  crystallizable  material  has  just  been  produced; 
in  fact  it  would  appear  that  a  considerable  degree  of  choice  may  be  exercised 
in  the  production  of  this  stearine  after  the  Halphen  test  response  is  gone. 

The  iodine  number  of  the  product  of  the  patent  is  not  stated  to  be  that  of  a 
product  in  which  the  response  to  Halphen  test  has  just  been  destroyed,  but  is 
that  of  a  product  in  which  both  conditions  have  been  met.  The  breadth  of  the 
range  given,  90  to  102,  indicates  that  "  the  desired  degree  of  crystallization " 
upon  ohilling  is  subject  to  considerable  variation,  according  to  the  object  in  view. 

The  other  distinguishing  mark  given  in  the  patent,  namely,  a  range  of  increase  in 
titre,  likewise  fails  to  disclose  any  definite  knowledge  of  the  degree  of  hydrogenation 
necessary  to  destroy  the  response  to  the  test;  its  indication  is  ambiguous  like  that 
of  the  iodine  number.  We  have  not  experimented  with  the  Wolfbauer  method, 
since  its  use  is  uncommon  in  this  country,  but  it  is  certain  that  the  range  of 
0.1°  to  0.5°  C.  represents  a  very  large  range  in  actual  hydrogenation,  as  mea- 
sured by  change  in  iodine  number.  It  is  noteworthy  that  our  experiments  in- 
variably showed  a  decrease  in  titre,  as  measured  by  the  A.  O.  A.  C.  method, 
before  any  increase  began,  so  that  to  increase  the  titre  0.1  to  0.5°  above  that 
of  the  original  oil  required  a  drop  of  iodine  number  to  about  70. 

We  wish  to  point  out  that  if,  as  Dr.  Lowenstein  asserts,  there  are  "  many  vari- 
able factors  which  would  have  an  effect  on  this  conclusion,"  there  exists  no  pub- 
*J.  Ind.  Eng.  Chem.,  9,  719. 


318  THE  HYDROGENATION   OF  OILS 

lished  evidence  to  that  effect.  It  seems  probable  to  us  that  temperature  is  the 
only  factor  which  would  have  such  an  effect,  and  the  temperature  150°  to  160°  C. 
was  specified  in  the  experiment  in  question. 

We  are,  therefore,  unable  to  agree  with  Dr.  Lowenstein's  implication  that  U.  S. 
Patent  No.  1,187,999  anticipates  our  disclosure.  It  is  quite  possible  that  other 
investigators  have  carried  out  the  same  work  at  an  earlier  date,  but  we  believe 
ourselves  to  have  been  the  first  to  publish  the  results  of  such  work." 

A  simple  method  for  the  detection  of  tallow  and  hydrogenated 
fats  in  butter  fat  is  proposed  by  Amberger.*  The  procedure  is 
based  upon  the  relative  insolubility  in  ether  of  tristearin  and  0- 
palmitodistearin  as  compared  to  the  other  glycerides. 

Pure  butter  fat  when  dissolved  in  a  certain  proportion  of  ether  forms  a  solu- 
tion which  deposits  no  crystals  when  kept  for  a  definite  time  at  a  certain  tem- 
perature. Under  these  conditions  the  presence  of  foreign  fats  containing  tristearine 
or  /3-palmitodistearine  is  shown  by  the  separation  of  crystals.  The  method  rec- 
ommended is  as  follows:  Weight  31  gm.  of  the  clear,  melted  (40°  to  50°)  fat  into 
a  100  cc.  volumetric  flask.  Fill  the  flask  to  the  mark  with  ether  and  cool  in  a 
water-bath  at  15°.  Mix  well  and  add  sufficient  ether  to  bring  the  level  of  the 
liquid  to  the  mark.  After  letting  stand  for  one  hour  in  the  bath  again  thor- 
oughly shake  the  mixture.  Repeat  the  shaking  after  another  hour.  If  only 
a  trace  or  no  deposit  has  formed  in  the  mixture  the  butter  is  pure  or  it  contains 
less  than  12  per  cent  of  tallow.  If  crystals  have  formed  filter  the  mixture  by 
means  of  suction  through  a  paper  disc  placed  upon  a  perforated  porcelain 
plate,  transferring  the  crystals  remaining  in  the  flask  by  means  of  3.4  cc.  of 
ether  containing  20  per  cent  alcohol.  Cover  the  funnel  containing  the  per- 
forated plate  and  continue  the  suction  until  the  crystals  are  drained  free  of 
liquid.  Transfer  the  crystals  to  a  tared  watch-glass  by  means  of  a  spatula  and 
allow  them  to  dry  at  room  temperature  or  heat  until  melted  to  remove  the  sol- 
vent. If  the  glycerides  recovered  in  this  manner  weigh  0.4  g.  or  over,  15  per 
cent  or  more  of  tallow  or  hydrogenated  fat  is  present.  A  considerable  number  of 
analyses  are  given  illustrating  the  value  and  limits  of  the  method.  In  case  the 
hydrogenation  process  has  been  very  incomplete  (iodine  number  reduced  less 
than  half),  the  product  cannot  be  detected  by  this  method,  but  in  other  cases 
their  detection  is  relatively  certain.  The  addition  of  15  per  cent  of  tallow  to 
butter  fat  gave  0.96  to  1.40  g.  of  crystallized  glycerides  and  larger  proportions 
yielded  correspondingly  greater  amounts. 

To  detect  carbon  disulphide,  hydrogen  sulphide,  and  other  compounds 
containing  sulphur  (albumin)  in  fats  and  oils,  Knorr  f  saponifies  the 
oil  with  concentrated  sodium  hydroxide,  salts  out,  and  the  liquor  from 
the  soap  is  tested  with  sodium  nitroprusside.  This  test  may  be  em- 
ployed in  examining  an  oil  to  determine  the  presence  of  sulphur  as  a 
catalyzer  poison. 

*Z.  Nahr.  Genussm.,  1916,  31,  297;  Chem.  Abs.,  1917,  1695;  Zeitsch  angew. 
Chem.,  1916,  29,  Ref.,  411;  J.  S.  C.  I.,  1916,  1077. 

t  Chem.  Zentr.,  1912,  2,  63;  from  Seifensieder-Zeit.,  1912,  39,  496;  J.  Chem.  Soc.,  1912, 
Abs.  102,  2,  990. 


CHAPTER   XIII 
EDIBLE   HYDROGENATED   OILS 

Since  the  addition  of  less  than  1  per  cent  of  hydrogen  suffices  to 
convert  cottonseed  oil  or  other  vegetable  oils  into  a  fatty  body  of 
at  least  the  consistency  of  lard,  it  follows  that  manufacturers  of 
ordinary  lard  compound  (that  is  to  say,  a  mixture  of  about  85  to 
90  per  cent  of  refined  cottonseed  oil  and  10  to  15  per  cent  or  so  of 
oleo-stearin)  have  promptly  turned  their  attention  to  the  production 
of  compound  by  a  "  self-thickened  "  cottonseed  oil. 

The  high  cost  *  of  oleo-stearin  prevailing  during  recent  years  makes 
the  method  an  attractive  one  and  the  hydrogenated  product  from 
cottonseed  oil  has  the  advantage,  if  properly  made,  of  being  very 
stable  in  character.  Unquestionably,  also,  the  hardening  process  is 
destined  to  increase  the  demand  for  cottonseed  oil  in  the  manufacture 
of  edible  fats.  [_^j 

By  the  hydrogenation  process  a  lard  substitute  may  be  prepared 
in  two  ways.  The  entire  oil  may  be  simply  hardened  to  the  consis- 
tency of  lard,  care  being  taken  to  employ  an  oil  as  nearly  neutral 
as  possible  to  prevent  excessive  solution  of  catalytic  metal,  and  to 
avoid  a  high  temperature  of  treatment  so  as  not  to  impair  the  flavor 
of  the  product.  If  the  color  and  flavor  are  detrimentally  affected, 
resort  may  be  had  to  a  further  treatment  with  fuller's  earth  followed 
by  steam-vacuum  deodorization.  The  addition  of  a  small  amount 
of  cocoanut  oil  benefits  the  flavor. 

The  other  method  is  that  of  making  lard  compound  which,  as  indi- 
cated above,  involves  thickening  a  large  proportion  of  normal  oil 
with  a  small  amount  of  a  relatively-hard  hydrogenated  product. 
This  may  be  carried  out  as  follows: 

After  the  oil  has  been  hardened,  it  is  freed  of  catalyzer  and  then 
may  be  run  into  tanks  containing  the  requisite  amount  of  deodorized 
cotton  oil  (or  other  edible  oil)  and  if  necessary  the  mixture  is  further 
clarified  and  filter-pressed.  With  hardened  cotton  oil  of  58  to  60 

*  Even  though  there  may  exist  no  marked  price  differential  between  oleo-stearin 
and  hardened  cottonseed  oil,  yet  when,  as  is  the  case,  millions  of  pounds  of  lard 
compound  are  made  monthly  in  this  country,  a  reduction  in  cost  of  but  a  small  frac- 
tion of  a  cent  per  pound  means  an  important  gross  saving. 

319 


320 


THE  HYDROGENATION  OF  OILS 


\ 


titer,  only  7  to  10  per  cent  is  required  to  thicken  the  oil  to  the  con- 
sistency of  lard,  although  in  hot  climates  a  somewhat  larger  propor- 
tion may  be  needed.*  The  mixture  is  run  onto  a  chill  roll  to  cause 
rapid  solidification  and  after  slight  aeration  to  improve  the  color 


FIG.  51, 


is  ready  to  be  packaged.     Fig.  51  shows  a  chill  roll  or  lard  cooler  of 
the  type  usually  employed. 

In  this  illustration  the  large  upper  cylinder  or  roll  is  chilled  by  the 
circulation  of  brine  and  is  slowly  rotated  say  from  6  to  10  r.p.m. 
The  hot  liquid  compound  at  a  temperature  of  50°  to  55°  C.  is  run 
into  the  feeding  trough  7  and  falls  onto  the  chilling  roll,  forming 
a  thin  somewhat  translucent  film  which  quickly  cools  and  solidifies. 
The  solid  fat  is  removed  by  a  scraper  and  falls  into  a  picker  trough  5. 
The  latter  contains  a  shaft  equipped  with  beating  and  conveying 
blades  which  churn  the  composition  and  destroy  the  translucency,  pro- 
ducing an  opaque  white  product  of  lard-like  appearance.  The  picker 
is  run  at  a  relatively  high  speed,  say  175  to  180  r.p.m.  Fig.  52  is 
an  end  view  showing  chill  roll,  feeding  trough  and  picker.  Fig.  53 
is  an  illustration  of  a  modified  type  of  compound  cooler.  In  Fig.  54 
the  cooler  and  picker  appear  on  the  left  hand  and  in  the  center  is  a  pump 
which  withdraws  the  product  from  the  picker  and  forces  it  through 
the  pipe  line  to  the  packaging  cocks  on  the  right  hand.  Too  high  a 

*  An  object  in  making  lard  compound  is  to  use  as  large  a  percentage  of 
cottonseed  oil  as  possible  and  yet  fulfil  the  required  conditions  as  to  the  stiffness 
of  the  material  to  withstand  warm  temperatures  without  much  softenino;.  Com- 
pound which  stands  a  moderately  warm  climate  can  be  made  with  even  as  low 
as  6  to  7  per  cent  hardened  oil. 


EDIBLE  HYDROGENATED  OILS 


321 


speed  of  the  picker  blades  incorporates  an  excessive  amount  of  air 
in  the  product  rendering  it  "  fluffy."* 

The  speed  of  rotation  of  the  chilling  roll  is  governed  by  the  rate  of 
feed  and  temperature  of  the  brine.  The  latter  may  be  kept  between, 
for  example,  —5  to  +10°F.  for  good  results.  If  the  brine  is  too 
cold,  the  product  is  liable  to  drop  badly  from  the  roll  and  the  texture 


END    VIEW. 

FIG.  52. 

is  not  always  satisfactory.  This,  however,  may  be  largely  remedied 
by  increasing  the  feed.  In  winter  the  brine  may  be  held  at  a  slightly 
higher  temperature  to  prevent  brittleness.  In  the  hottest  weather, 
very  cold  brine  should  be  used  to  aid  in  securing  a  product  which  will 
preserve  its  color  and  consistency  for  a  considerable  time. 

When  properly  made  the  compound  derived  by  the  hydrogenated 
oil  thickener  is  excellent  in  color,  texture,  flavor  and  keeping  qual- 
ities. By  many  it  is  considered  superior  in  several  respects  to  oleo- 
stearin  compound. 

*  The  author  desires  to  make  acknowledgment  to  the  Allbright-Nell  Co.  of 
Chicago  and  the  Brecht  Co.  of  St.  Louis  for  their  courtesy  in  furnishing  the  illustra- 
tions Figs.  51  to  54. 


322 


THE  HYDROGENATION  OF  OILS 


Possibly,  however,  for  best  results  as  to  stability  it  is  desirable  to 
hydrogenate  the  entire  body  of  oil  to  a  fatty  acid  titcr  of  36  or  38, 
or  whatever  consistency  may  be  required,  rather  than  to  take  a  rela- 
tively small  proportion  of  the  oil  and  harden  it  to  a  titer  of  50  to  60 


FIG.  53. 


or  thereabouts  and  incorporate  with  unhydrogenated  oil.  It  appears 
that  the  hydrogenation  of  the  total  body  of  the  oil,  by  transforming 
the  linoleic  and  linolenic  compounds  and  the  like,  has  a  tendency  to 
improve  the  oil  as  regards  its  edibility  and  certainly  gives  it  greater 
stability.  The  flavor  of  lard  compound  is,  however,  preferred  by 


FIG.  54. 

many  large  users  of  lard  substitute  presumably  because  of  the  pro- 
portion of  normal  oil  which  it  contains,  and  the  manufacturing  cost 
is  lower. 

Finally,  it  may  be  stated,  by  partial  saturation  of  glycerides,  we 
have  the  possibility  of   preparing   from  tri-olein  the   oleo-distearin 


EDIBLE  HYDROGENATED   OILS  323 

or  the  dioleostearin.  Dioleopalmitin  would  give  either  oleostearo- 
palmitin  or  distearopalmitin.  From  tri-olein  we  may  have  the  two 
isomeric  oleo-distearins,  a-  and  /3-oleo-distearin  as  well  as  a-  and 
/3-dioleostearin.  Which  of  these  we  may  be  able  to  produce  control- 
lably  and  which  may  prove  best  from  the  edible  standpoint  are  problems 
for  the  future  to  solve. 

Joslin*  calls  attention  to  the  economy  in  using  hardened  oil  "  vege- 
table stearin"  in  place  of  oleo-stearin  for  making  lard  compound, 
since  only  7  to  10  per  cent  of  the  former  is  called  for  against  14  to 
20  per  cent  of  the  oleo-stearin.  Of  course  the  amount  of  hardened 
oil  required  depends  on  its  degree  of  •  "  hardness  "  but  for  the  present 
grades  of  hydrogenated  cottonseed  oil  of  58  to  60  titer,  now  on 
the  market,  the  above  proportions  hold.  When  the  oil  is  hardened  to 
about  the  consistency  of  average  oleo-stearin,  naturally  a  greater  pro- 
portion is  needed  in  lard  compound. 

Joslin  notes  the  resultant  economy  by  the  employment  of  hardened 
oil  at  one  plant  during  a  period  of  one  year. 

93  parts  cottonseed  oil  at  6.45 $6.00 

7  parts  hardened  oil  (vegetable  stearin)  at  9.25 .65 

Cost  per  hundred  pounds,of  compound $6 . 65 

86  parts  cottonseed  oil  at  6.45 $5 . 55 

14  parts  oleo-stearin  at  9.25 1.29 

Cost  per  hundred  pounds  of  compound $6 . 84 

Or  a  saving  of  practically  20  cents  per  hundred  pounds  of  compound 
manufactured. 

Hydrolecithin  has  been  prepared  from  lecithin  by  Riedel.f  A  hard- 
ened fat  called  "Brebesol"  intended  for  edible  purposes  is  manufac- 
tured by  the  Bremen  Besigheimer  Olfabriken.t 


EDIBILITY  OF  HYDROGENATED  OILS 

It  seems  to  be  generally  accepted  by  those  who  have  investigated 
the  matter  carefully  that  the  hydrogenated  oils  have  as  desirable  a 
degree  of  edibility  as  the  oils  from  which  they  are  derived.  It  is  even 
claimed  that  by  destroying  traces  of  certain  unsaturated  bodies 
thought  to  be  slightly  toxic  in  nature,  hydrogenation  renders  the  oil 
better  adapted  for  human  consumption. 

*  National  Provisioner  1914,  17. 

t  Method  of  Preparing  Hydrolecithin.     German  Patent.     Compare  Paal  and 
Oehme,  Ber.,  1913,  1297. 
J  Seifen.  Ztg.,  1914,  263. 


324  THE  HYDROGENATION  OF  OILS 

A  question  of  serious  import  has,  however,  arisen  in  the  use  of 
nickel  catalyzer.  Aside  from  the  fact  that  by  careless  nitration 
traces  of  the  suspended  nickel  may  be  present  in  the  product,  there 
is  the 'more  serious  problem  of  the  actual  solution  of  nickel  to  form 
nickel  soaps  which  cannot  be  easily  removed. 

According  to  Bomer,*  nickel  is  dissolved  by  oils  during  the  hydro- 
genation  treatment  only  when  the  oil  contains  free  fatty  acid  in 
considerable  amounts.  A  sample  of  hydrogenated  sesame  oil  con- 
taining 2}  per  cent  of  fatty  acid  was  found  to  contain  0.01  per  cent 
ash  with  0.006  per  cent  nickel  oxide.  Whale  oil,  containing  0.6  per 
cent  fatty  acid,  yielded  0.006  per  cent  ash  and  0.0045  per  cent  nickel 
oxide.  Such  an  amount  of  nickel  possibly  would  be  regarded  as  unde- 
sirable or  objectionable  in  a  product  intended  for  edible  purposes. f 

*  Zeitsch.  Nahr.  Genussm.  (1912),  104  and  Chem.  Rev.  u.  d.  Fett.  u.  Harz.  Ind. 
(1912),  221. 

t  In  a  discussion  of  Bomer's  paper  (loc.  cit.)  Lehmann  asked  whether  nickel 
was  found  in  sufficient  amounts  to  make  a  quantitative  determination  in  hydro- 
genated oils,  and  Bomer  replied  that  the  amount  of  nickel  was  just  so  much  larger 
the  greater  the  amount  of  free  acid  in  the  oil  and  the  longer  the  action  of  the  catalyzer 
on  the  oil;  while  Prall  observed  that  the  nickel  content  of  hardened  oil  depended 
essentially  upon  the  amount  of  free  acid  and  that  one  should  reduce  the  free  fatty 
acid  to  the  lowest  possible  amount,  that  with  0.2  per  cent  free  fatty  acid  in  the  oil 
no  nickel  had  been  detected  in  the  hardened  products  examined.  One  could  say, 
however,  that  in  100  grams  of  oil  a  fraction  of  a  milligram  of  nickel  is  detected. 
Lehmann  then  remarked  that  presumably  it  was  to  be  understood  that  the  presence 
of  nickel  could  not  be  avoided  and  that  one-half  a  milligram  of  nickel  in  100  grams 
of  the  oil  would  be  a  good  result,  to  which  Prall  replied  that  this  was  the  case  when 
the  acid  of  the  oil  was  well  removed. 

Auerbach  (Chcm.  Ztg.,  37,  297)  regards  the  0.000002  per  cent  or  so  of  nickel 
which  remains  in  hydrogenated  oil  to  be  of  no  practical  moment  from  the  stand- 
point of  edibility. 

An  oil  mill  in  Europe  making  high-grade  peanut  oil  is  now  constructing  a  plant 
for  hardening  edible  oils  by  a  hydrogenation  process  that  is  said  to  afford  a  product 
free  from  the  objectionable  traces  of  nickel  found  in  most  of  these  oils.  The  hardened 
oil  will  be  sold  to  the  margarine  factories. 

Lehmann  stated  (Bomer,  loc.  cit.)  that  we  need  have  no  great  concern  over  the 
utility  of  this  fat  or  of  its  physiological  action;  Straub  noted  that  samples  of  the 
hardened  oil  melted  at  53°  C.  and  that  fats  of  such  high  melting  point  or  in  fact  any 
fat  melting  above  37°  C.  were  not  suitable  for  persons  affected  with  certain  maladies 
of  the  digestive  tract.  Lehmann  remarked  that  the  work  carried  on  in  the  Voit  labo- 
ratory indicated  high  melting  point  fats  to  be  injurious,  but  considering  the  way 
hardened  fats  are  made,  apparently  the  means  were  at  hand  to  make  the  melting 
point  high  or  low  at  will;  that  fats  which  were  to  be  eaten  must  not,  of  course,  have 
a  melting  point  of  53°  C.  Bomer  added  that  he  was  of  the  opinion  that  hardened 
fats  were  not  as  beneficial  as  oil,  but  that  was  not  the  question.  The  widespread 
use  of  edible  oils  depended  on  the  fact  that  edible  fats  must  have  a  certain  measure 
of  consistency.  Margarine  melting  at  20  degrees  required  but  a  slight  addition  of 


EDIBLE  HYDROGENATED  OILS  325 

The  use  of  nickel  in  the  form  of  an  oxide,  or  the  use  of  nickel  catalyzer 
containing  a  considerable  proportion  of  oxide,  is  perhaps  undesirable 
from  the  point  of  view  of  solubility  in  oil.  Nickel,  in  the  metallic 
state,  cannot  combine  with  a  fatty  acid  to  produce  a  soap,  except 
with  the  elimination  of  hydrogen,  and  in  the  presence  of  an  atmosphere 
wholly  of  hydrogen,  because  of  mass  action,  such  reaction  would  not 
be  likely  to  take  place.  On  the  other  hand,  nickel  in  the  form  of 
oxide  would  yield  water  on  combining  with  fatty  acid  which  would  be 
yielded  practically  into  a  vacuum  as  regards  the  vapor  pressure  of 
water.  Hence  in  the  manufacture  of  products  intended  for  edible 
purposes  it  is  suggested  that  conditions  be  maintained  such  that  the 
catalyzer,  if  of  the  nickel  type,  is  preserved  almost  wholly  in  the 
metallic  state.  Also  it  is  desirable  to  not  force  the  reaction  too 
rapidly  with  the  consequent  danger  of  breaking  down  the  carboxyl 
group  and  setting  free  water  which  would  react  to  produce  fatty  acid.* 

a  fat  melting  at  50  degrees.  It  was  not,  therefore,  a  question  of  the  melting  point 
of  the  hardened  oil,  but  of  the  melting  point  of  the  margarine  or  other  edible  fat 
and  the  hardened  oil  was  employed  simply  to  adjust  the  melting  point,  the  same  way 
as  beef  tallow  and  the  like  were  used. 

A  synopsis  of  Bomer's  paper  (Z.  Nahr.  Genussm.,  24,  104-113)  appearing  in 
Chemical  Abstracts,  Nov.  10,  1912,  3201,  concisely  expresses  his  work.  Samples 
of  peanut,  sesame,  cottonseed  and  whale  oil  were  hardened.  The  analyses  of  the 
resulting  products  indicate  that  the  more  completely  unsaturated  fatty  acids  (oleic, 
linolenic  and  linoleic)  are  converted  into  stearic  with  increase  in  the  melting  point 
and  the  lowering  of  the  iodine  number,  while  the  saponification  number  is  scarcely 
altered.  The  iodine  number  of  the  liquid  acids  seems  to  indicate  that  the  less  satu- 
rated acids  are  more  rapidly  converted  into  stearic  than  is  oleic.  The  partially 
saturated  products  resemble  lard  in  color,  taste  and  odor,  while  those  obtained  by 
further  hardening  are  very  similar  to  beef  or  mutton  tallow.  The  ordinary  constants 
of  the  hardened  peanut  oil  are  so  similar  to  those  for  lard  that  it  is  very  difficult  to 
distinguish  it  from  hog  fat,  but  the  phytosterol  of  the  3  vegetable  oils  investigated 
was  not  affected  by  the  treatment,  so  that  the  phytosterol  acetate  test  may  be 
relied  upon  for  the  detection  of  these  artificially  hardened  fats  when  they  are  used 
as  adulterants  for  lard,  margarine,  etc.  Cottonseed  oil,  after  treatment,  no  longer 
gives  the  Halphen  reaction,  but  sesame  oil  still  responds  to  the  Baudouin  test. 
Where  nickel  is  the  catalytic  agent  traces  of  it  will  be  found  in  the  finished  product 
if  there  were  any  appreciable  amount  of  free  acid  in  the  original  oil.  Bomer  con- 
cludes with  a  brief  report  of  preliminary  work  on  the  stereo-chemistry  of  the  glycer- 
ides  formed  and  the  requirements  which  the  new  product  will  have  to  meet  to  be 
acceptable  as  a  human  food. 

*  Bouant  (La  Galvanoplastie  (1894),  186)  makes  the  comment  that  after  having 
considered  nickel  as  dangerous  in  the  preparation  of  food,  it  is  now  recognized, 
on  the  contrary,  to  be  harmless.  Langbein  (Electro  Deposition  of  Metals  (1909), 
246)  observes  that  hot  fats  strongly  attack  nickel.  (Trans.  Am.  Electrochem. 
Soc.,  23,  116  (1913).) 

In  the  course  of  some  investigations  by  Gates  (J.  of  Phys.  Chem.  (1911),  15, 


326  THE   HYDROGENATION   OF  OILS 

The  investigations  of  various  authorities,  such  as  Lehmann,  Thorns 
and  Miiller  have  shown  that  hardened  oils  used  for  edible  purposes  do 
not  cause  any  derangement  of  the  system  and  that  they  are  the  complete 
equivalent  of  animal  and  vegetable  fats  of  like  melting  point.*  Hydro- 
genated  fats  are  used  just  like  ordinary  fats  and  do  not  hinder  the 
assimilation  of  other  food  constituents.  The  nickel  content  on  a  daily 
consumption  of  100  grams  of  the  hardened  fat  is  stated  to  amount 
at  the  most  to  0.6  mg.  and  may  be  regarded  as  entirely  uninjurious. 
Hardened  fat  possesses  extremely  good  keeping  qualities,  and  this  is 
probably  also  the  case  with  margarine  prepared  from  it.f  Leimdorfer 
observes  that  hydrogenated  fats  change  in  odor  and  color  when  pre- 
served even  in  a  vacuum.  J 

A  careful  study  of  the  occurrence  of  nickel  in  edible  products  of 
various  kinds  has  been  made  by  Normann  and  Hugel.§  Hardened 
fats  prepared  with  the  aid  of  nickel  catalyzers,  and  intended  for  edible 
purposes,  contain  traces  of  nickel  which  they  state  amounts  to  two 
parts  per  million.  But  fats  which  have  been  treated  in  nickel-lined 
receptacles  show  fully  this  content  of  nickel.  Nickel-lined  ware  has 

97)  it  was  observed  that  many  of  the  common  metals  are  dissolved  appreciably  by 
oleic,  palmitic  and  stearic  acids,  with  evolution  of  hydrogen. 

The  Bureau  of  Animal  Industry  of  the  Department  of  Agriculture  is  investigat- 
ing the  matter  and  apparently  intends  to  determine  the  relative  degree  of  toxicity 
of  the  traces  of  nickel  in  the  form  existing  in  improperly  made  hydrogenated  oil. 
We  may  add  that,  so  far  as  can  be  ascertained,  the  Department  looks  kindly  upon 
the  advent  of  hydrogenated  oil  in  view  of  the  likelihood  that  it  is  destined  to  prove 
a  very  acceptable  substitute  for  higher-priced  animal  fats  and  does  not  propose, 
according  to  our  understanding,  to  venture  any  ruling  until  the  matter  has  had 
protracted  scrutiny. 

The  editor  of  the  National  Provisioner  comments  on  the  foregoing  as  follows: 

"It  is  evident  that  the  government  investigations  have  resulted  favorably,  since 
stearine  made  by  this  process  is  recognized  and  passed  by  the  Bureau  in  meat  inspec- 
tion, the  only  requirement  being  that  it  shall  be  stated  on  the  label  that  it  is  '  Stearine 
made  from  cottonseed  oil'  to  indicate  that  it  is  manufactured  stearine  rather  than 
the  natural  article."  Editorial  note  in  National  Provisioner,  Dec.  27,  1913. 

Thompson  notes  that  some  criticism  has  been  directed  at  the  use  of  hardened 
oils  for  edible  purposes  on  the  ground  that  nickel  is  used  in  the  process,  but  the 
manufacturers  say  that  although  nickel  is  generally  used  none  of  it  is  left  in  the  oil, 
and  that  even  if  it  were  it  is  harmless,  as  shown  by  many  tests  with  animals  and 
with  human  "poison  squads."  Consular  &  Trade  Reports,  Dept.  of  Commerce,  Jan. 
14,  1914,  171. 

*  See  also  "Gehartete  Pflanzenfette  in  der  Speisefettindustrie,"  Der  Seifen- 
fabrikant,  1914,  181. 

t  Halbmonatsschr.  f.  d.  Margarine-Ind.,  1914,  No.  4,  37;  Seifen.  Ztg.,  1914,  206. 

t  Seifen.  Ztg.,  1913,  1317;  J.S.C.I.,  1914,  206. 

§  Seifen.  Ztg.,  1913,  959. 


EDIBLE  HYDHOGENATED   OILS  327 

been  in  use  for  ten  years  or  more  and  during  this  period  many  people 
have  eaten  foodstuffs  containing  nickel,  without  any  injurious  effects 
being  noted.     Two  publications  have  already  discussed  the  matter      , 
to  some  extent,  one  being  by  Ludwig*  and  the  other  by  Lehmann.f       \ 
In  one  kilo  of  various  foodstuffs  these  investigators  found  the  follow- 
ing content  of  nickel: 

Ludwis  Lehmann 

Spinach 25-27  mgs.    Beef  and  bouillon 26-64  mgs. 

Peas 12-16     "       Potato   pulp    (equal  part 

Lentils  (acid) 35     "          of  water) 26-40 

Lentils  (boiled) 24     "      Spinach 22.4 

Sourkraut   54-129     "      Damson  plum  mixture ...  13.3 

Plums 35     "      Sourkraut 18-57 

Fruit  cooked  in  2  per  cent 

acetic  acid  solution ....     65-67 
Water,    salt    water,    flesh 

extract  and  milk 3.5-5.3 

The  whole  question  appeared  of  sufficient  importance  to  lead  Nor- 
mann  and  Hugel  to  repeat  this  work.  They  used  a  nickel  kettle  to 
prepare  the  food  material  and  ignited  the  product  in  a  silica  vessel 
to  obtain  the  content  of  ash.  Hydrochloric  acid  was  then  added  to 
the  ash  and  the  nickel  determined  by  Tschugaeff's  reagent.  J  In  this 
manner  the  nickel  was  determined  gravimetrically  in  all  cases,  with 
the  exception  of  coffee.  In  this  latter  case  a  colorimetric  comparison 
with  a  nickel  solution  of  known  content  was  made. 

Thus  Normann  and  Hugel  found : 

Duration  of  Mgs.  of  nickel 

cooking,  in  one  kilo  of 

hours  material 

Coffee \  0.03 

Apple \  46 

Cabbage f  83 

Red  cabbage 1  67 

Sourkraut \\  127 

Kohlrabi 1  19 

Potato 1  80 

One  of  these  investigators  used  a  kettle  of  this  character  for  a 
considerable  period  in  his  household.  The  food  for  the  use  of  the 
family  was  cooked  in  the  kettle  so  that  food  with  a  nickel  content, 
approximating  that  of  the  above  tabulation,  was  eaten,  but  no  ill 
effects  were  observed. 

*  Osterr.  Chem.  Ztg.,  Vienna,  Vol.  I,  No.  1,  1898. 
t  Arch,  fur  Hygiene,  Vol.  68  (1909),  421. 
\  Zeitsch.  f.  angew.  Chem.,  1907,  1844. 


328  THE  HYDROGENATION   OF  OILS 

The  determination  of  nickel  in  fats  was  made  by  igniting  200  grams 
of  the  fat  in  a  silica  vessel,  dissolving  the  ash  in  hydrochloric  acid, 
saturating  the  solution  with  ammonia,  filtering  to  remove  any  pre- 
cipitate of  iron  or  alumina  and  evaporating  the  filtrate.  To  the 
residue  was  added  1  cc.  of  Tschugaeff's  reagent  (alcoholic  solution  of 
dimethylglyoxime)  and  ammonia  (when  a  rose  coloration  due  to  nickel 
occurs).  To  determine  the  nickel  quantitatively,  the  whole  residue 
was  dissolved  in  100  cc.  of  water  and  the  coloration  compared  with 
the  color  produced  by  adding  the  reagent  to  solutions  of  nickel  chloride 
of  known  content.  To  secure  a  constant  shade  it  was  found  desirable 
to  allow  the  solution  as  well  as  the  standard  to  stand  for  some  time, 
usually  over  night,  before  final  observations  were  made. 

Of  seven  samples  of  hardened  cottonseed  oil  examined,  four  samples 
contained  0.03  mg.  of  nickel  in  one  kilo.  One  sample  showed  a  rela- 
tively high  content,  0.075  mg.  of  nickel;  while  the  remaining  samples 
contained  0.02  mg.  of  nickel.  Palm  kernel  oil  showed  a  content  of 
nickel  ranging  from  0.017  to  0.1  mg.  of  nickel  per  kilo,  averaging 
around  0.02  mg.  Thus  it  will  be  noted  that  the  nickel  content  of 
these  fats  is  only  about  one-thousandth  part  of  that  found  in  foods 
prepared  in  nickel  kettles,  and  when  one  considers  that  fats  generally 
are  not  used  for  edible  purposes,  by  themselves,  but  simply  as  additions 
to  other  foods,  the  amount  of  nickel  furnished  by  hydrogenated  fatty 
material  amounts  to  so  very  little  that  the  consumption  of  such  food 
year  in  and  year  out  may  be  regarded  as  harmless. 

Even  in  fats  intended  for  technical  purposes,  the  amount  of  nickel 
is  small  as  compared  with  that  found  in  the  food  materials  above 
mentioned,  as  for  example: 

Nickel  in  one  kilo 

Hardened  fish  oil 3.3    mgs. 

Hardened  fish  oil 1.2    mgs. 

Hardened  fish,  oil 3.2    mgs. 

Hardened  cottonseed  oil 0.85  mgs. 

Meyerheim*  notes  that  oils  which  are  to  be  hardened  for  edible  pur- 
poses  should  be  washed  with  alkali  to  remove  fatty  acid  in  order  to 
reduce  the  tendency  to  solution  of  nickel  by  the  oil;  also  that  care 
should  be  taken  in  filter  pressing  to  completely  eliminate  the  particles 
of  nickel  catalyzer. 

The  propriety  of  using,  for  edible  purposes,  low-grade  fats  which 
have  been  deodorized  and  cleansed  by  hydrogenation  has  been  made 
the  subject  of  considerable  debate.  Bohm  states  f  that  when  Mege 

*  Fortschr.  Chem.  Phys.  and  Phys.  Chem.,  1913,  305. 
t  Seifen.  Ztg.  (1912),  1087. 


EDIBLE  HYDROGENATED  OILS  329 

Mouries  was  working  on  the  production  of  artificial  butter  it  was  far 
from  his  mind  to  use  low-grade  fats  which  had  been  purified  by  chem- 
ical treatment  and  that  Boudet  prescribed  only  fat  of  the  best  quality 
obtained  from  cattle  slaughtered  on  the  same  day.  Later  when  Huet 
claimed  to  make  an  edible  product  by  thorough  treatment  of  bad 
tallow  with  aluminium  chloride  solution,  the  margarine  industry  was 
hit  a  severe  blow;  for  after  such  a  proposal  the  opponents  of  artificial 
butter  sought  and  with  good  results  to  prejudice  the  public  against 
margarine. 

Although  to-day  in  a  margarine  establishment  there  is  to  be  found  the  uttermost 
cleanliness  as  regards  the  plant,  Bohm  states  that  this  is  not  true  of  the  raw  material 
before  it  comes  into  the  hands  of  the  margarine  manufacturer.  Even  though,  he 
declares,  development  of  oil  hardening  may  mean  a  great  advance  technically,  it 
is  coupled  with  such  an  opportunity  for  the  employment  of  low-grade  raw  materials 
that  it  is  likely  to  cause  anxiety  on  the  part  of  the  public.  In  particular  Bohm 
refers  to  the  utilization  of  hardened  fish  oil  in  the  margarine  industry  in  which 
application  technically  it  appears  entirely  suitable.  Hardened  fish  oil,  he  states, 
is  to  be  sure  a  chemically-changed,  completely  bacteria-free  product;  and  physio- 
logically is  uninjurious.  If,  however,  according  to  Bohm,  we  are  to  sanction  the 
chemical  treatment  of  fish  oil,  this  would  establish  an  important  precedent  for  the 
application  of  all  sorts  of  by-product  fats  and  cadaver  fats.  When  Hefter,  together 
with  other  experts,  formulated  for  the  margarine  industry  the  restriction  that  only 
those  fats  should  be  used  which  had  been  obtained  from  animals  slaughtered  under 
inspection,  every  consumer  as  well  as  every  manufacturer  of  margarine  was  affected. 
With  the  inauguration  of  margarine  manufacture  from  fish  oil  Bohm  further  states 
it  appears  not  improbable  that  conflict  with  the  present  laws  will  arise. 

Bohm  refers  to  the  assertion  of  Loock  regarding  renovated  butter  to  the  effect 
that  no  person  who  realizes  the  unpleasant  properties  of  the  original  material  would 
buy  such  butter,  a  statement,  says  Bohm,  which  can  certainly  apply  equally  well 
to  whale  oil  margarine.  Loock  also  cites  a  decision  to  the  effect  that  no  doubt 
exists  that  a  food  product  is  to  be  looked  upon  as  unfitted  for  consumption  when 
the  raw  material  possesses  a  loathsome  nature,  irrespective  as  to  whether  the  material 
through  chemical  treatment  has  been  freed  from  such  undesirable  properties. 

As  to  the  loathsome  nature  of  whale  oil,  Bohm  asserts  that  one  need  only  note 
the  character  of  the  methods  employed  in  obtaining  it  in  order  to  appreciate  its 
undesirable  nature.  He  maintains  that  a  great  part  of  the  carcasses  of  whales  are 
allowed  to  stand  days  at  a  time  before  they  are  worked  up.  Bohm  indignantly 
declares  the  proposal  to  make  an  edible  fat  out  of  half-rotten  whales  which  are 
treated  in  the  hovels  of  the  natives  must  naturally  excite  disgust.  Perhaps,  he 
says,  a  manufacturer  of  artificial  butter  may  be  able  to  use  hardened  fish  oils  in 
spite  of  the  pure  food  laws,  but  may  yet  come  into  contact  with  the  criminal  courts, 
for  when  one  buys  margarine  he  expects  to  obtain  freshly  prepared  beef  fat  and  not 
a  chemically-changed  fish  oil. 

While  this  contention  of  Bohm  may  not  be  sound  in  some  respects 
it  is  noted  here  for  the  sake  of  completeness.  Naturally  such  an 
attack  against  a  new  and  promising  use  for  whale  oil  has  not  passed 


330  THE  HYDROGENATION  OF  OILS 

unnoticed.  See  rejoinder  by  Lieber  in  Seifensieder  Zeitung  (1912), 
1188,  and  editorial  comment  adverse  to  Bohm,  also  the  opinion  of 
Keutgen.* 

An  oil  which  has  been  used  so  extensively  by  physicians  all  over 
the  world  as  a  remedial  food  for  children  Lieber  believes  cannot  be 
looked  upon  as  unsafe  for  human  consumption.  He  calls  attention 
to  the  hardy  nature  of  the  Eskimo  whose  principal  or  sole  food  is  the 
blubber  of  the  whale  and  seal.  Furthermore,  he  contends  that  if 
the  carcasses  of  whales  were  allowed  to  decompose,  the  oil  which 
resulted  would  be  of  low  grade  and  the  pecuniary  loss  would  be  con- 
siderable. By  the  present  system  as  soon  as  a  whale  is  harpooned 
it  is  hoisted  aboard  the  whaling  ship  and  immediately  rendered,  the 
several  grades  of  oil  obtained  being  pumped  to  separate  tanks.  Every 
effort  is  made  to  produce  the  maximum  yield  of  No.  0  and  No.  1  oil 
because  of  the  relatively  high  prices  these  bring. 

Until  seven  years  ago  there  was  only  a  limited  demand  for  whale 
oil,  which  was  mainly  used  for  the  production  of  glycerine  and  fatty 
acids.  It  is  now  hydrogenated,  for  soap-making  purposes,  but  in 
OfferdahPs  opinion  hardened  whale  oil  is  suitable  for  food.  With 
regard  to  the  traces  of  nickel  present  in  the  hardened  oil,  experiments 
showed  that  when  small  amounts  of  nickel  powder  were  taken  daily 
no  ill  effects  were  experienced,  and  that  99.8  per  cent  of  the  metal 
was  rapidly  excreted  from  the  system.  Hardened  whale  oils  were 
found  to  be  free  from  bacteria. t 

The  Halbmonatschrift  f.  d.  Margarineindustrie  (Dusseldorf)  discusses  the  ques- 
tion of  the  prohibition  of  the  use  of  whale  oil  in  the  edible  fat  industry  (Seifen.  Ztg. 
(1914),  30)  and  from  this  discussion  the  following  is  noted, t  —  Ever  since  the  dis- 
covery was  made  of  preparing  an  odorless  and  tasteless  fat  from  whale  oil  by  the 
hardening  process  it  has  been  taken  for  granted  in  those  circles  which  are  antago- 
nistic to  the  further  development  of  the  margarine  and  artificial  edible  fat  industry 
that  hardened  fish,  seal  or  whale  oil  could  be  used  in  the  preparation  of  butter  sub- 
stitutes. This  suspicion  was  all  the  greater  because  of  the  increase  in  the  last  few 
years  in  the  cost  of  most  of  the  raw  materials  used  in  the  margarine  industry.  It 
has  been  customary  for  the  agricultural  opponents  of  butter  substitutes  to  condemn 
the  raw  products  from  which  these  products  are  obtained  and  in  this  way  to  seek 
to  make  this  indispensable  article  of  food  repulsive  to  the  consumer.  But  in  recent 
years  the  knowledge  that  margarine  practically  does  not  influence  the  price  of 
natural  butter,  and  therefore  does  not  enter  into  competition  with  it,  has  gained 
some  little  headway.  Dr.  Vieth,  Director  of  the  Dairy  Station  in  Hameln  (an 
authority  in  his  line)  has  acknowledged  this  to  be  a  fact.  If  the  margarine  does  not 

*  Seifen.  Ztg.  (1914),  89. 
t  Offerdahl,  Ber.  (1913),  558. 

j  See  also  the  views  of  the  Deutsche  Margarine  Zeitschrift  (Seifen.  Ztg.  (1914), 
118). 


EDIBLE  HYDROGENATED  OILS  331 

harm  the  butter  industry,  the  bottom  is  taken  out  of  the  agitation  which  has  been 
going  on  for  over  a  decade  against  the  manufacture  of  substitutes.  In  spite  of 
this  (Molkerei  Zeitung,  1913)  space  has  been  lent  anew  to  the  suspicion  that  the 
raw  materials  used  in  the  production  of  margarine  cannot  be  entirely  without  effect. 

Edible  fats,  such  as  hardened  palm-kernel  oil,  cottonseed  oil,  etc.,  which  have 
recently  been  introduced  into  the  manufacture  of  margarine  are  thoroughly  tested 
by  government  officials  and  scientific  experts.  The  suspicion  that  infectious  raw 
materials  might  be  utilized  can  therefore  apply  only  to  the  possible  use  of  hardened 
whale  and  seal  oil.  In  order,  however,  to  prevent  the  spread  of  this  idea  and  in 
order  thereby  to  prevent  a  new  danger  to  the  butter  substitute  industry,  the  Duessel- 
dorfer  Margarine  Zeitschrift  suggests  a  legal  prohibition  of  the  use  of  whale  oil  in 
the  edible  fat  industry. 

It  is  supposed  that  the  official  foodstuff  investigators  will  eventually  aid  this 
proposal.  Its  necessity  is  shown  by  the  fact  that  an  effort  has  been  made  from 
foreign  countries  to  induce  German  margarine  factories  to  use  whale  oil.  The 
suggestion  that  well-known  and  reputable  margarine  factories  have  already  started 
to  use  whale  oil  has  been  shown  to  be  without  foundation  and  is  thought  to  be 
out  of  the  question  for  the  future.  In  order  that  no  margarine  made  from  whale 
oil  may  reach  the  German  consumer  because  of  unscrupulous  manufacturers  (and 
in  that  way  the  good  name  of  a  product  which  has  been  established  only  after  many 
years  of  effort  be  brought  into  ill  repute)  but  one  remedy  can  be  suggested:  the 
prohibition  of  whale  oil  for  food  purposes.  The  trade  journal  of  the  margarine 
industry  points  out  that  such  a  value  is  placed  by  all  classes  of  society  upon  mar- 
garine that  the  thought  of  utilizing  any  raw  material  repulsive  to  individual  consumers 
ought  to  meet  with  vigorous  opposition.  It  is  evident  from  the  editorial  comment 
at  the  close  of  this  article  that  the  Seifensieder  Zeitung  is  not  in  accord  with  the 
drastic  views  expressed  in  the  foregoing.* 

On  the  subject  of  hydrogenated  edible  oils  but  little  has  appeared 
in  the  literature.f  A  number  of  patents  discuss  various  products  and 
methods  of  preparation. 

An  edible  oil  composition  is  described  by  Ellis  J  comprising  hydro- 
genated cottonseed  oil  and  cocoanut  oil,  the  mixture  being  beaten 
with  air  to  improve  the  color  of  the  product.  The  following  formula 
and  method  of  treatment  are  given:  Ninety  parts  cottonseed  oil  are 
mixed  with  ten  parts  of  cocoanut  oil  and  the  mixture  subjected  to  the 
action  of  hydrogen  at  a  temperature  of  from  150°  to  160°  C.,  in  the 
presence  of  finely-divided  nickel  so  as  to  convert  a  large  proportion 
of  the  unsaturated  into  saturated  material.  A  solid  composition  is 
produced  which  is  then  subjected  to  aeration  which  may  be  carried 
out  by  beating  the  hydrogenated  product  with  rapidly  revolving 

*  Further  comment  by  Keutgen  on  the  same  subject  appears  in  Seifen.  Ztg. 
(1914),  171. 

t  In  an  article  on  "Hydrogenated  or  Hardened  Fat,"  appearing  in  the  National 
Provisioner,  Sept.  27,  1913,  104,  Hall  observes  that  hydrogenation  is  one  of  the 
greatest  advances  ever  made  in  the  fat  and  oil  field. 

t  U.  S.  Patent  1,037,881,  Sept.  10,  1912. 


332  THE  HYDROGENATION  OF  OILS 

paddles  until  a  sufficient  quantity  of  air  is  incorporated  in  the  product, 
in  a  finely-vesiculated  condition  to  produce  a  material  of  the  proper 

\  consistency  and  light  colored  appearance.  Another  statement  *  gives 
details  of  a  hydrogenated  butter  substitute  in  which  various  hydro- 
genated  and  normal  oils  are  incorporated  to  make  a  fat  approximating 
the  melting  point  of  butter,  with  which  is  mixed  milk,  etc.,  to  produce 
a  variety  of  margarine.  These  compositions  should  ordinarily  have 
a  melting  point  considerably  less  than  the  temperature  of  the  human 
body,  so  that  when  the  material  is  taken  into  the  mouth,  it  immedi- 
ately melts  and  does  not  leave  a  greasy  sensation  on  the  tongue  and 
walls  of  the  mouth.  It  is  generally  desirable  to  carry  the  hydrogena- 
tion  treatment  to  a  point  where  a  product  of  rather  firm  consistency 
is  secured.  This  produces  a  material,  however,  which  is  of  too  high 
a  melting  point  for  the  production  of  a  vegetable  butter  composition. 
Hence  it  is  then  pressed  to  remove  the  excessive  amount  of  stearin. 
In  the  case  of  cottonseed  oil,  it  is  stated  that  it  is  desirable  to  hydro- 
genate  until  the  iodine  number  falls  to  about  80.  The  oil  may  then 
be  cooled  to  about  30°  C.,  and  allowed  to  stand  for  a  time  and  pressed. 
Afterwards  it  is  warmed  to  render  it  entirely  fluid,  and  is  incorporated 
with  milk  material.  Suitable  material  of  this  character  is  ordinary 
full  milk  or  skim  milk  or  butter-milk,  sterilized  milk,  sour  milk  or 
milk  which  has  been  specially  fermented.  Coloring  material,  such 
as  ordinary  butter  color,  may  be  added.  Also  a  flavoring  compound, 
such  as  cumarin  and  various  esters  and  aldehydes,  such  as  those  of 
valerian  and  capryl  bodies,  may  be  added.  In  order  to  give  the  prod- 
uct the  property  of  browning,  when  heated  in  a  skillet,  bodies  such 
as  egg  yolk,  milk  sugar,  lecithin  or  finely-powdered  casein  may  be 
introduced. 

A  suitable  oil  base  having  been  derived  in  this  manner,  the  oily 
material  is  emulsified  with  the  milk  material  to  thoroughly  mix  the 
latter  with  the  fatty  body.  For  100  parts  of  fatty  material  about 
30  to  60  parts  of  full  milk  or  perhaps  50  to  80  parts  of  skim  milk  are 
suitable  proportions.  In  the  summer  months  a  stiffer  composition  is 
required  than  in  the  winter  months  and  the  fatty  material  should  be 
compounded  to  give  a  material  melting  at  the  proper  point  with 
reference  to  seasonal  temperatures.  In  emulsifying  it  is  desirable 
to  put  a  portion  of  the  milk  in  the  beating  apparatus,  and  to  stir  for 
a  short  time.  In  the  case  of  full  milk,  beating  for  10  minutes  or  so 
causes  a  separation  of  the  butter  fat.  The  oil  may  then  be  added  in 
portions,  beating  thoroughly  until  the  composition  is  well  incorpo- 

v  rated.     The  remainder  of  the  milk  and  fatty  material  may  be  added 
*  Ellis,  U.  S.  Patent  1,038,545,  Sept.  17,  1912. 


EDIBLE  HYDROGENATED  OILS  333 

from  time  to  time,  and  the  temperature  of  the  mixture  should  prefer- 
ably be  maintained  between  30°  and  40°  C.  When  the  composition 
has  become  thoroughly  incorporated,  it  is  run  from  the  apparatus  into 
a  cooling  device  which  cools  the  emulsified  composition  rapidly.  It  is 
then  ready  to  be  rolled  and  kneaded  to  remove  the  excess  of  water, 
etc.,  after  which  treatment  the  material  is  formed  into  the  desired 
shape  for  shipment.  The  coloring  material  and  salt  and  also  flavoring 
material  may  be  added  during  the  emulsification  process  if  desired. 

The  use  of  hardened  oil  in  preparing  oleomargarine  compositions 
is  the  basis  of  French  Patent  458,611,  of  1913,  to  Deveaux. 

Hydrogenated  soya  bean  oil  *  has  been  recommended,  as  well  as 
hydrogenated  vegetable  oil  and  animal  fats  mixed  to  form  lardjike 
products  of  varying  composition.  When  employing  cocoanut  oil  in 
such  compositions  it  is  desirable  to  hydrogenate  it.  To  be  sure,  cocoa- 
nut  oil  usually  has  an  iodine  value  of  only  7  to  10,  which  is  indicative 
of  the  small  proportion  of  unsaturated  bodies  present.  But,  in  spite  of 
this,  in  order  to  secure  a  permanent  product,  which  does  not  separate 
or  grow  lumpy  on  standing,  and  which  remains  in  a  perfectly  neutral 
condition  for  a  long  period  of  time,  even  when  exposed  to  the  air,  it 
is  desirable  that  the  iodine  number  of  the  cocoanut  oil  should  be 
reduced  to  practically  zero,  if  larger  proportions  than  30  per  cent  or 
thereabout  are  incorporated  with  hydrogenated  soya  bean  or  cotton- 
seed oil. 

An  edible  product  of  a  superhydrogenated  character  f  is  obtained 
by  carrying  the  degree  of  hydrogenation  beyond  the  actual  titer  re- 
quired and  then  pressing  to  remove  some  of  the  harder  material  so 
that  the  final  titer  of  the  expressed  fat  is  that  of  lard,  butter  or  what- 
ever other  titer  may  be  required.  Most  oils  of  a  vegetable  nature 
and  some  animal  oils  contain  from  traces  up  to  considerable  quantities 
of  highly-unsaturated  bodies,  including  those  of  the  linoleic  and  lino- 
lenic  group.  These  and  other  similar  bodies  are  very  sensitive  to 
oxidation  and  lend  instability  to  edible  oil  products  of  this  character 
by  their  tendency  to  change  chemically  and  thus  alter  the  flavor  of 
the  material.  These  bodies  may  be  saturated  by  very  careful  hydro- 
genation up  to  the  degree  of  consistency  required  in  the  edible  prod- 
uct, but  such  hydrogenation  is  difficult  to  carry  out  commercially  on 
a  large  scale  with  the  assurance  that  the  product  will  run  uniform  in 
quality.  By  saturating  these  bodies  with  hydrogen  to  an  excessive 
degree  as  regards  final  consistency,  these  bodies  lose  their  identity 
and  become  substantially  free  of  odor  of  origin  and  tendency  to  rancid- 

*  Ellis,  U.  S.  Patent  1,047,013,  Dec.  10,  1912. 
t  Ellis,  U.  S.  Patent  1,058,738,  April  15,  1913. 


334  THE  HYDROGENATION  OF  OILS 

ify  or  otherwise  be  decomposed.  By  hydrogenating  cottonseed  or 
corn  oil  or  similar  oils  to  materially  reduce  the  iodine  number,  the 
more  sensitive  double  bonds  are  saturated  with  hydrogen  and  thereby 
eliminated  and  oxidation  tendency  is  reduced  to  a  minimum.  Ap- 
parently the  complete  elimination  of  all  the  double  bonds  character- 
istic of  the  linoleic  type  is  more  difficult  than  the  removal  of  the  double 
bonds  characteristic  of  the  linolenic  type,  so  that  control  over  this 
seeming  selective  action  during  hydrogenation  when  saturating  up 
to  a  given  degree  of  consistency  from  a  given  oil  is  difficult,  if  not 
impossible,  under  ordinary  conditions  of  hydrogenating.  If,  however, 
the  oil  is  overhydrogenated  so  that  a  more  consistent  fat  is  acquired 
than  is  actually  desired  for  an  edible  product,  the  unstable  bodies 
thus  may  be  completely  transformed.  In  order  to  secure  the  degree 
of  consistency  desired  the  hot  hydrogenated  fat  is  gradually  cooled 
to  about  30°  C.,  when  the  temperature  may  be  maintained  between 
25°  to  35°  C.,  or  so  for  several  hours  to  induce  crystallization  or  ball- 
ing of  the  high  melting  point  compounds.  The  mass  is  then  pressed 
to  the  desired  degree.  Such  a  superhydrogenated  pressed  product 
which  may  be  made  either  of  butter-like  or  of  lard-like  consistency 
is  stable  in  storage  and  is  not  liable  to  coagulate  on  standing  with 
the  formation  of  objectionable  masses  of  granulous  stearin-like 
bodies. 

It  has  been  noted  when  a  vegetable  oil  such  as  cottonseed  oil  is 
hydrogenated  directly  until  of  the  consistency  desired  that  on  cool- 
ing frequently  it  tends  to  granulate  unless  chilled  or  very  rapidly 
cooled.  This  is  objectionable  in  culinary  operations  as  an  initial 
lard-like  body  after  once  heating  and  slow  cooling  in  the  air  often 
forms  relatively  hard  granules  of  stearin-like  bodies  which  look  like 
little  balls  of  coagulated  material  and  separating  as  they  do  from  the 
fluid  oil  under  some  circumstances  give  the  product  the  appearance  of 
having  curdled  or  decomposed.  By  super-hydrogenating  and  press- 
ing to  the  point  required  the  granulating  stearins  or  stearin-like  bodies 
are  eliminated  to  a  greater  or  less  extent  and  less  easily  crystal- 
lizing or  non-granulating  stiffening  bodies  remain  tending  from  their 
amorphous  texture  to  better  maintain  the  original  consistency  and 
appearance  of  the  product  in  repeated  culinary  use. 

The  Boyce  process  *  of  producing  an  edible  compound  consists  in 
preparing  a  mixture  of  synthetic  stearin  by  the  action  of  hydrogen 
in  the  presence  of  a  catalyzer  upon  a  previously  unsaturated  oil  or 
fat,  the  latter  being  subjected  to  the  catalytic  action  of  hydrogen  to  a 

*  Boyce,  U.  S.  Patent  1,061,254,  May,  6,  1913,  assigned  to  the  American  Cotton 
Oil  Co. 


EDIBLE  HYDROGENATED  OILS  335 

degree  sufficient  to  convert  the  required  fraction  of  the  oil  into  syn- 
thetic stearin.  The  hydrogcnation  process  is  arrested  at  the  point 
when  the  stearin  is  found  to  be  present  in  the  amount  of  about 
20  per  cent  of  the  entire  body  of  the  oil.  Boyce  states  that  by  arrest- 
ing the  action  at  this  point  there  will  remain  a  mixture  of  the  unsatu- 
rated  oil  and  the  synthetic  stearin  produced  by  the  hydrogenation 
of  a  portion  of  the  oil. 

A  hydrogenated  fatty  food  product  containing  hydrogenated  corn 
oil  has  been  described.*  When  corn  oil  is  suitably  hydrogenated,  a 
product  is  derived  which  has  the  property  of  improving  the  stability 
of  hydrogenated  cottonseed  oil  or  similar  hydrogenated  oils  which 
tend  to  granulate.  Also  it  is  stated  that  hydrogenated  cocoanut  oil 
may  be  used  as  a  fluxing  agent  for  chocolate  in  the  manufacture  of 
confectionery.  The  melting  point  of  the  fatty  flux  should  preferably 
be  about  90°  to  100°  F.  Hydrogenated  cocoanut  oil  olein  may  be 
used  in  a  similar  manner.  The  manufacture  of  the  coating  of  choco- 
late creams  calls  for  a  relatively  high  melting  point  fat  which  incor- 
porates readily  with  chocolate  and  does  not  impair  its  flavor.  Cocoa 
butter  is  especially  desired  on  this  account,  but  is  relatively  expensive. 
Cocoanut  oil  melts  so  easily  that  in  hot  weather  candies  made  with  it 
soften  very  quickly  when  handled.  Cocoanut  oil  also  has  a  tendency 
to  rancidify.  By  hydrogenation  of  an  oil  assimilable  with  chocolate 
the  exact  melting  point  desired  may  be  obtained  and  a  stable  compo- 
sition secured. 

Hydrogenated  oil  of  high  titer,  as  stated,  may  be  mixed  with  un- 
hydrogenated  oil  to  form  a  body  of  a  consistency  suitable  for  use  as 
a  substitute  for  lard.  For  example,  hydrogenated  cotton  oil  of  a  titer 
of  say  52°  C.  (fatty  acids)  may  be  melted  and  incorporated  with  four 
times  its  weight  or  so  of  ordinary  refined  or  deodorized  cottonseed 
oil  so  as  to  form  on  cooling  a  white,  opaque  fatty  material  of  the  con- 
sistency of  ordinary  lard.  The  product  made  in  this  manner  is  not 
always  sufficiently  stable.  Not  infrequently  in  a  short  time  it  will 
lose  its  opacity  to  a  considerable  degree  and  will  take  on  an  appear- 
ance more  suggestive  of  petrolatum  than  lard.  Sometimes  this  change, 
which  may  be  due  to  a  tendency  to  form  solid  solutions  of  certain 
types,  occurs  irregularly  in  layers  or  isolated  zones  which  give  the 
product  a  curious  mottled  appearance,  and  this  striated  effect  taking, 
place  in  the  containers  during  storage  so  changes  the  product,  physically 
at  least,  that  it  is  regarded  as  damaged  or  unfit  for  use  by  those  accus- 
tomed to  the  normal  appearance  of  lard.  By  disseminating  through 
a  fatty  basis  of  a  melting  point  and  consistency  approaching  that  of 
*  Ellis,  U.  S.  Patent  1,067,978,  July  22,  1913. 


336  THE  HYDROGENATION  OF  OILS 

lard,  a  quantity  of  fatty  material  of  higher  titer  so  as  to  form  floccula- 
tions  of  a  high  titer  product  uniformly  disseminated  through  the 
fatty  basis,  a  product  of  better  "  color  stability  "  is  secured.*  The 
material  of  the  relatively  higher  titer  may  be  denominated  the  stabilizer 
and  the  proportions  of  fatty  basis  and  stabilizer  as  well  as  their  melt- 
ing points  and  titers  may  be  varied  to  meet  various  conditions  of  a 
climatic  nature. 

As  an  illustration  one  may  take  to  make  the  fatty  basis,  6  parts  of  hydrogenated 
cottonseed  oil  of  a  titer  ranging  between  52°  to  54°  C.  (fatty  acids)  and  34  parts  of 
refined  and  deodorized  cottonseed  oil.  A  thorough  mixture  is  secured  by  the  aid 
of  heat  and  when  well  incorporated  the  melted  product  is  chilled  rapidly  in  a  thin 
layer  by  feeding  onto  a  chilled  roll  which  is  kept  in  constant  rotation  and  from  which 
the  solidified  product  is  removed  in  layers  by  a  scraper.  This  product  when  prop- 
erly set  has  a  consistency  approaching  that  of  ordinary  lard.  The  stabilizer  is  pre- 
pared by  incorporating  3  parts  of  hydrogenated  cottonseed  oil  of  the  same  titer  as 
that  used  in  making  the  fatty  basis,  with  5  parts  of  refined  and  deodorized  cottonseed 
oil.  By  heating  the  hardened  oil  with  the  deodorized  oil  the  requisite  mixture  is 
obtained.  As  in  making  the  fatty  basis,  the  stabilizer  is  likewise  chilled  to  form  a 
solid,  preferably  in  thin  layers,  and  the  two  products  are  mixed  in  powerful  mixing 
apparatus  until  the  stabilizer  is  well  disseminated  through  the  fatty  basis.  To 
secure  a  desirable  distribution  both  the  fatty  basis  and  the  stabilizer  may  be  fed 
onto  the  same  chill  roll  in  a  series  of  adjacent  or  alternate  streams,  or  the  fatty 
basis  may  be  allowed  to  fall  on  the  chill  roll,  and  when  it  has  progressed  a  distance 
sufficient  to  solidify  but  not  to  stiffen  it  fully,  the  stabilizer  is  applied  as  a  super- 
posed coating  adherent  to  and  slightly  intermingled  at  the  contacting  surfaces, 
with  the  fatty  basis.  This  composite  film  is  removed  by  the  scraper  and  is  then 
"pugged"  or  beaten.  As  the  melting  point  of  the  stabilizer  is  preferably  consider- 
ably higher  than  that  of  the  fatty  basis,  the  former  congeals  more  quickly,  so  that 
although  the  superposed  film  is  somewhat  insulated  from  the  chill  roll  by  the  fatty 
basis  film  yet  the  solidification  of  the  upper  layer  is  usually  rapid  enough  to  prevent 
material  solution  or  interfusion  of  the  two  heterogeneous  layers. 

Further  modifications  are  the  following:  Eighty  parts  of  cottonseed  oil  are  mixed 
with  fifteen  parts  of  hydrogenated  oil  of  a  titer  of  48 ,  (fatty  acids) .  This  is  chilled 
and  mixed  with  five  parts  of  melted  42°  C.  titer  hydrogenated  or  hard  oil,  or  fat. 
Likewise  one  can  superpose  on  a  basis  of  34  to  38  titer  about  20  per  cent  of  40  to 
42  titer.  Cottonseed  oil  may  be  hydrogenated  to  37  titer,  chilled  as  described  and 
similarly  incorporated  with  about  10  to  20  per  cent  cottonseed  oil  hydrogenated 
to  40  to  42  titer.  Thus  there  may  be  obtained  a  lard-like  or  otherwise  consistent 
fatty  material  having  its  main  titer  to  a  considerable  degree  influenced  so  that  the 
product  may  have  the  desired  soft  consistency  of  ordinary  lard  while  actually  con- 
taining bodies  which  if  melted  into  the  fatty  basis  would  raise  the  melting  point 
and  consistency. 

Palm  oil,  suitably  hydrogenated,  has  been  recommended  for  use 
in  edible  fat  products,  f 

*  EUis,  U.  S.  Patent  1,070,331,  Aug.  12,  1913. 
t  EUis,  U.  S.  Patent  1,087,161,  Feb.  17,  1914. 

The  fatty  acids  of  Kaya  oil  have  been  hydrogenated  by  Ueno  (Chem.  Rev.  u. 
d.  Fett.  u.  Harz.  Ind.  (1913),  209)  who  thereby  obtained  fatty  acids  melting  at 


EDI  HI, K    IIYDROGENATED   OILS  337 

Wilbuschewitsch  *  regards  his  process  as  applicable  to  the  treat- 
ment of  all  unsaturated  acids  and  their  glycerides,  as  well  as  for 
waxes  and  other  alcoholic  fatty  substances.  From  castor  oil  there  is 
obtained  a  product  which  melts  at  83°  C.  The  finished  fat  can  be 
hydrolyzed  and  the  fatty  acids  distilled.  For  example,  from  cotton- 
seed oil  there  may  be  obtained  fatty  acids  which  melt  up  to  71°  C. 
and  make  excellent  candles.  After  suitable  refining  the  products 
may  yield  satisfactory  alimentary  fats  if  the  reduction  is  only  carried 
so  far  that  the  melting  point  is  between  28°  and  34°  C.  Thus  he 
finds  from  castor  oil  there  may  be  made  a  product  which  is  odorless 
and  tasteless  but  retains  the  other  properties  of  castor  oil.  So  also 
from  cod  liver  oil  and  other  fish  oils  there  may  be  made  butter  substi- 
tutes, or  from  vegetable  oils  substitutes  for  cocoa  butter.  Oils  treated 
by  the  process  lose  their  specific  odor.f 

It  has  been  shown  by  Erlandsen,  Fridricia  and  Elgstromt  that  hardened  whale 
oil  is  eminently  suitable  as  a  human  food.  Experiments  were  made  with  the  whale 
fat  in  comparison  with  butter  fat.  The  apparent  digestibility  ranges  from  91.6 
to  94.9  per  cent  for  these  two  fats  and  the  difference  between  butter  and  whale  oil 
does  not  exceed  0.9  per  cent.  A  margarine  containing  22.8  per  cent  of  the  whale 
oil  was  used  in  an  institution  where  250  people  were  fed.  A  physician  who  was 
in  constant  attendance  reported  favorable  results. 

A  sample  of  butter  fat  examined  by  Amberger§  contained  only  2.4  per  cent  of 
triolein.  By  fractional  crystallization  of  the  glycerides  of  hydrogenated  butter  fat, 
it  was  found  that  the  olein  had  not  been  converted  into  tristearin,  but  into  a  mixed 
glyceride.  The  greater  part  of  the  oleic  acid  in  butter  fat  is  therefore  present  as  a 
mixed  glyceride  and  not  as  triolein.  Butyric  and  caproic  acids  are  also  present  as 
mixed  glycerides;  tributyrin  and  tricaproin  could  not  be  isolated  from  the  fat. 
Butyrodiolein,  butyro-  palmito-olein,  and  oleodipalmitin  are  present,  as  is  shown 
by  analysis  of  the  glycerides  isolated  from  the  alcohol-soluble  portion  of  hydro- 
genated butter  fat.  Amberger  has  also  isolated  another  glyceride,  m.pt.  67.9°  C., 
from  butter  fat;  this  glyceride  yielded  a  mixture  of  fatty  acids,  m.pt.  55.5°  C.  (See 
page  318.) 

65.5°  C.  The  hydrogenation  of  the  material  was  carried  out  in  alcohol  solution  using 
platinum  black  as  a  catalyzer.  Kaya  oil  as  employed  for  edible  purposes  is  liquid 
and  yellow  in  color. 

*  U.  S.  Patent  1,024,758,  April  30,  1912. 

t  The  keeping  properties  of  some  hardened  oils  examined  by  Knapp  (Analyst, 
1913,  102)  were  found  to  be  remarkably  good.  Although  prepared  nearly  a  year 
and  a  half  previously,  and  having  often  been  exposed  to  damp  air,  yet  these  samples 
showed  no  signs  of  rancidity.  The  acidity  (0.7  per  cent  as  oleic  acid)  did  not  appre- 
ciably change  during  the  period  of  observation. 

tTidskrift  Kern.  1918,  15,  109;  Chem.  Abs.  1918,  1793. 

§  Z.  Unters.  Nahr.  Genussm.,  1918,  35,  313;  J.  S.  C.  I.,  1918,  558A. 


CHAPTER  XIV 
EDIBLE  HYDROGENATED   OILS— Continued 

Wesson  *  observes  that  one  of  the  latest  contributions  of  the 
chemist  has  been  the  hydrogenization  of  fatty  oil  which  converts 
it  into  a  solid  fat  by  the  introduction  of  hydrogen  into  the  molecules 
of  the  unsaturated  acids.  This  enables  the  manufacturer  of  cooking 
fats  to  turn  out  compounds  consisting  entirely  of  vegetable  fat. 
which  are  fast  displacing  the  mixtures  of  oil  with  animal  fats  for- 
merly employed.  By  the  new  process  of  hydrogenation  wholesome 
edible  fats  of  the  consistency  of  butter  and  lard  are  now  produced 
entirely  from  what  normally  will  probably  continue  to  be  our  cheapest 
vegetable  oil,  namely,  cottonseed  oil. 

A.  H.  Gill  f  discusses  the  subject  of  hardened  oils  in  their  various 
applications.  Concerning  edible  products  obtained  by  hydrogenation, 
he  observes  that 

It  is  claimed  for  them  that  they  can  be  heated  hotter  (to  455°  F.)  without 
smoking  than  ordinary  fat:  this  cooks  the  outside  of  the  food  more  quickly  and 
prevents  the  grease  from  soaking  in.  Consequently  it  is  less  greasy,  more 
digestible,  dry  and  crisp:  Another  advantage  is  that  no  odor  is  absorbed;  fish, 
onions  and  potatoes  can  be  cooked  successively  in  the  same  fat.  Another  •  claim 
is  that  one-fourth  less  is  used  of  these  fats  than  of  butter;  further  that  it  is  all 
fat,  while  butter  contains  5  to  16  per  cent  of  water. 

Gill  also  notes  that  hydrogenated  vegetable  oils  seem  to  offer  a  satisfactory 
substitute  for  animal  fats  to  those  who  object  to  the  latter  from  prejudice  or 
religious  scruples. 

Klimont  and  Mayer  J  consider  the  chief  objections  against  the  use 
of  hydrogenated  fish  oil  in  the  manufacture  of  margarine  are  that 
the  production  of  the  crude  fish  oil  is  not  under  proper  control, 
that  the  disagreeable  odor  may  reappear  when  the  product  is  kept 
for  a  long  time,  that  the  hydrogenated  oil  may  contain  small  quan- 
tities of  nickel,  and  that  it  has  a  higher  melting-point  than  any  of 
the  fats  hitherto  used  for  foods  and  hence  would  probably  not  be 
easily  digested. 

*  J.  Ind.  Eng.  Chem.,  1915,  277. 

t  Science  Conspectus,  Mass.  Inst.  Tech.,  1915,  Vol.  V,  No.  4. 
J  Z.  angew.  Chem.,  1914,  27,  645;  J.  S.  C.  I.,  1915,  148. 
338 


EDIBLE  HYDROGENATED   OILS  339 

Klimont  and  Mayer  were  unable  to  detect  nickel  in  hydrogenated  oil  exam- 
ined by  them;  hence  this  test  could  not  be  relied  upon  for  the  detection  of 
hardened  fish  oil  in  oleomargarine.  The  following  test  is  proposed:  2  to  3  g. 
of  the  sample  is  melted,  and  dissolved  in  acetone  to  a  total  volume  of  50  cc. 
After  standing  for  twelve  hours  at  the  ordinary  temperature,  the  crystals  which 
separate  then  are  filtered  off,  dried  and  weighed.  Oleomargarine  yields  12  to  13 
per  cent  of  crystals  of  M.P.  45°  to  47°  C.  In  the  case  of  artificial  mixtures  of 
oleomargarine  with  hydrogenated  fish  oil  and  rape  oil,  the  portion  crystallizing 
from  acetone  was,  in  all  cases,  considerably  greater  than  12  to  16  per  cent,  which 
may.be  taken  as  the  limits  for  genuine  oleomargarine.  It  was  possible  by  this 
test  to  detect  3.5  per  cent  of  hardened  fish  oil  when  this  was  added,  together  with 
5.5  per  cent  of  rape  oil,  to  olemargarine. 

Initially,  Bontoux  states,  edible  peanut,  cotton,  sesame  and  sun- 
flower oil  were  hardened  for  use  as  edible  fats  in  margarine  manu- 
facture but  with  the  perfection  of  the  hydrogenation  process,  lower 
grade  oils  including  No.  0  and  No.  1  whale  oil  were  hardened.* 

A  plea  for  the  prohibition  of  hardened  whale  oil  in  oleomargarine 
is  made  by  a  number  of  German  margarine  concerns,!  who  base 
their  petition  on  the  inedible  character  of  the  original  oil. 

Bergius  J  notes  that  a  careful  survey  of  the  applicability  of 
hardened  fats  for  edible  purposes  fails  to  discover  anything  objec- 
tionable in  such  products. 

The  food  value  of  hydrogenated  oils  has  been  studied  by  Pekel- 
haring  and  Schut.§  White  rats  and  mice,  and  a  dog,  were  used  in 
these  experiments.  The  fats  fed  were  hydrogenated  whale,  peanut, 
sesame  and  cottonseed  oils.  Frequent  determinations  of  the  fat 
content  of  the  feces  were  made,  and  the  general  condition,  changes 
in  weight,  etc.,  of  the  animals  noted.  The  investigators  conclude 
that  these  fats  are  not  only  harmless,  but  may  well  find  applica- 
tion as  human  food  and  that  they  give  best  results  when  mixed  with 
natural  fats,  as  lard. 

Thorns  and  Muller  1 1  have  made  an  extensive  study  of  the  chemical 
and  physical  properties  and  physiological  action  of  peanut,  cotton- 
seed and  other  oils  which  have  been  altered  by  the  hardening 
process  so  that  they  have  a  higher  melting-point.  Feeding  experi- 
ments on  man  and  animals  indicate  that  they  are  harmless  and  are 
to  be  considered  as  useful  articles  of  diet. 

Holmes  and  Lang  have  published  a    paper  entitled    "  Fats  and 

*  Matures  Grasses,  1914,  4194;   Siefen.  Ztg.,  1914,  987. 

t  Seifen.  Ztg.,  1914,  604;  Margarine  Industrie,  1914. 

j  Seifen.  Ztg.,  1914,  728. 

§  Pharm.  Weekblad,  53,  769-85,  1916;  Chem.  Abs.,  1916,  2758. 

II  Arch.  Hyg.,  84,  56-77,  1915;  Chem.  Abs.,  1915,  1642. 


340  THE  HYDROGENATION  OF  OILS 

V 

their  Economical  Use  in  the  Home/'*  in  which  they  refer  to  the 
edible  grades  of  hardened  vegetable  fats.  They  state  that  hardened 
oils  used  in  this  field  are  generally  white  in  color,  have  no  appre- 
ciable odor  or  taste  and  are  less  likely  to  become  rancid  than  the 
original  oil.  They  also  state  that  a  number  of  these  fats  marketed 
under  a  variety  of  trade  names  have  proved  popular  and  appear 
to  be  of  quite  wide  application.  It  is  observed  that  the  hardening 
process  may  be  of  special  value  in  the  future  utilization  of  some  oils 
like  fish  oils  which  because  of  objectionable  flavors  or  odors  are  not 
entirely  suited  for  edible  purposes  in  their  natural  state. 

Estabrook  f  advocates  a  product  for  edible  purposes,  consisting 
of  wheat  flour  mixed  with  comminuted  hardened  oil. 

This  product,  when  made  into  a  dough  by  the  addition  of  milk  or  water,  and 
baked,  is  shortened  by  the  presence  of  the  hardened  fatty  material. 

The  shortening  agent  Estabrook  states  is  made  according  to  the  following 
process:  cottonseed  oil  is  first  heated  and  nickel  salt  is  added  thereto.  Hydrogen 
is  then  conducted  into  the  oil,  and  the  heat  is  continued  and  mass  the  stirred 
constantly.  The  nickel  salt  acts  as  a  catalyzer^  causing  the  oleic  acid  of  the  oil 
to  take  up  hydrogen,  whereby  it  is  changed  into  stearic  acid.  When  the  process 
of  hydrogenation  has  progressed  far  enough  to  give  the  mass  the  desired  hard- 
ness, which  is  ascertained  by  making  a  titre  test,  the  melted  fat  is  filtered  off 
from  the  nickel  and  allowed  to  cool.  The  product  thus  obtained  is  stated  to  be 
much  harder  than  natural  hard  fats,  and  due  to  the  changes  produced  by  the 
hydrogenation  process  it  will  keep  for  an  indefinite  length  of  time  without 
becoming  rancid.  This,  Estabrook  explains,  as  due  to  the  fact  that  the  linolein 
of  the  oil,  which  tends  to  produce  rancidity,  is  changed  by  the  process  into 
stearin.  Freedom  from  rancidity  he  states  is  also  due  in  a  large  measure  to  the 
fact  that  the  hardened  oil  contains  little  or  no  olein,  practically  all  of  the  oleic 
acid  of  the  oil  being  converted  to  stearic  acid  by  the  process  described;  and  any 
palmitin  which  may  be  present  is  unobjectionable  for  the  reason  that  this  is 
a  solid  and  lends  itself  readily  to  the  preparation  of  a  dry-shortening  flour. 

The  hardened  oil  is  finely  ground  and  mixed  with  flour.  For  the  purpose 
of  making  biscuit  or  a  similar  product  Estabrook  states  that  about  12  Ib.  of  the 
comminuted  hardened  oil  should  be  mixed  with  200  Ib.  of  flour.  The  product 
may  be  sacked  or  barreled,  for  shipping  purposes,  and,  as  indicated  above,  may 
be  kept  for  an  indefinite  length  of  time  without  material  deterioration.  Baking 
powder  also  may  be  added  to  the  flour,  as  well  as  seasoning,  so  that  for  cooking 
purposes  it  is  only  necessary  to  make  a  dough  of  the  product  by  adding  milk 
or  water,  rolling  it  into  a  relatively  thin  mass  and  then  cutting  into  biscuits  and 
baking.  For  making  pie  crust,  or  similar  types  of  pastry,  Estabrook  recom- 
mends the  amount  of  hardened  oil  added  to  the  flour  to  be  about  24  Ib.  to  200 
Ib.  of  flour,  and  the  leavening  agent  to  be  omitted.  In  making  ordinary  baker's 
bread  the  proportion  is  about  5  Ib.  of  the  comminuted  hardened  oil  to  200  Ib. 
of  fiour. 

*  Bulletin  No.  469,  Department  of  Agriculture. 

f  J.  S.  C.  I.,  1914,  1218;  U.  S.  Patent  No.  1,117,012,  November  10,  1914.  See  also 
Nos.  1,276,507,  1,276,508  and  1,276,509  issued  August  20,  1918  to  Ellis. 


EDIBLE  HYDROGENATED  OILS  341 

Kohman,  Godfrey  and  Ashe  employ  hydrogenated  fats  in  the  man- 
facture  of  bread.* 

A  shortening  effect  equal  in  value  to  that  produced  by  relatively  large  quan- 
tities of  liquid  oil  is  stated  to  be  obtained  by  the  employment  of  a  hard  fat, 
which  also  permits  the  use  of  sufficient  water  not  only  to  supply  the  amount 
required  for  giving  stiffness  and  springiness  to  the  dough,  but  to  supply,  in  the 
baked  loaf,  the  quantity  recognized  as  desirable  for  imparting  to  the  bread  the 
expected  freshness  and  flavor.  The  employment  of  the  hard  fat  as  the  shortening 
agent  is  likewise  found  to  add  to  the  keeping  qualities  of  the  loaf,  in  the  sense 
that  even  after  the  loaf  has  lost  its  original  freshness,  it  lacks  the  rancidity 
frequently  met  with  in  ordinary  bread  which  has  been  kept,  under  the  same  con- 
ditions, for  the  same  period  of  time.  For  the  present  purpose  they  use  as  the 
shortening  agent,  a  hard  fat  of  either  vegetable  or  animal  origin, — as,  for  instance 
hydrogenated  edible  vegetable  oil  (hydrogenated  cottonseed  oil),  hydrogenate, 
edible  animal  oil,  or  oleo-stearin.  Kohman,  Godfrey  and  Ashe  give  preference 
to  the  use  of  hydrogenated  cottonseed  oil,  or  other  hydrogenated  vegetable  oil 
of  an  edible  character,  for  the  stated  reason  that  such  oils  are  relatively  cheap, 
and  can  be  hydrogenated  or  hardened  up  to  a  high  melting-point  readily  and 
conveniently.  Thus  hardened  cottonseed  oil  having  a  melting-point  of  57°  C. 
is  well  adapted  for  shortening  purposes. 

To  incorporate  the  hard  fat  of  high  melting-point  into  the  dough  batch  it  is 
desirable  to  bring  the  former  first  into  intimate  admixture  with  flour.  This  may 
be  effected  by  melting  the  hard  fat  and  heating  it  somewhat  above  its  melting- 
temperature  and  then  mixing  the  flour  therewith.  The  heating  and  mixing  opera- 
tion may  be  carried  out  in  a  rotary  drum,  having  a  heating  jacket,  and  provided 
with  stirrers.  The  temperature  should  be  maintained,  during  the  mixing  opera- 
tion, above  the  melting-point  of  the  fat,  so  that  the  flour  shall  not  chill  the  mass, 
or  the  flour  may  be  preheated,  for  the  same  purpose.  It  is  found  that  under 
these  conditions  a  quantity  of  flour  equal  in  weight  to  from  5  to  10  times  the 
weight  of  the  melted  fat  will  absorb  the  fat,  and  that  the  flour  will  retain  its  pul- 
verulent condition.  The  procedure  involves  heating  only  a  relatively  small 
quantity  of  the  flour.  Thus,  if  1  Ib.  of  hard  fat  is  to  be  added  to  a  dough 
batch  containing  880  Ib.  of  flour,  it  will  suffice  to  absorb  the  fat  in  5  to  10  Ib. 
of  flour,  in  the  manner  described,  and  it  is  found  that  in  the  subsequent  mixing 
and  kneading  of  the  dough  batch,  the  shortening  thus  added  to  the  relatively 
small  amount  of  flour  will  be  uniformly  distributed  throughout  the  entire  mass. 
This  feature  avoids  heating  the  entire  mass  of  flour  up  to  the  temperature  of  the 
small  portion  which  has  absorbed  the  fat. 

The  hard  fat  may  also  be  incorporated  with  the  flour  in  the  manner  following: 
The  melted  fat  heated  to  a  temperature  of  200°  C.  and  upward  may  be  supplied 
from  a  suitable  melting  and  heating  receptacle  to  a  discharge  pipe  from  which 
it  may  be  ejected,  at  a  correspondingly  high  temperature,  in  the  form  of  a 
fine  spray  or  cloud,  by  a  jet  of  air  into  an  inclosed  chamber.  Into  this  chamber 
the  flour  may  be  sifted,  and  on  coming  in  contact  with  the  highly  heated  par- 
ticles of  fat  sprayed  into  the  chamber,  take  up  the  fat.  The  flour  thus  impreg- 
nated with  the  melted  fat  remains  in  a  pulverulent  condition,  after  cooling,  and 
is  available  for  use  as  a  part  of  the  flour  ingredient  of  the  dough  batch.  In 

*  U.  S.  Patent  Nos.  1,204,280  and  1,204,281,  November  7,  1916. 


342  THE  HYDROGENATION  OF  OILS 

this  case  it  is  found  that  by  repeating  the  absorbing  operation  a  number  of 
times,  upon  the  same  body  of  flour  a  quantity  of  flour  from  five  to  ten  times  the 
weight  of  the  fat  is  sufficient  to  absorb  the  fat  and  yet  remain  in  a  pulverulent 
condition. 

It  is  found  that,  with  equally  good  results  as  to  color,  texture  and  expansion,  a 
quantity  of  the  melted  fat  incorporated  with  the  flour  in  either  of  the  ways  de- 
scribed may  be  employed  of  approximately  one-twentieth  the  weight  of  the  cotton- 
seed oil  used  ordinarily  in  making  up  the  dough  batch.  Thus,  in  those  instances 
where  from  2  to  3  per  cent  of  cottonseed  oil  (calculated,  by  weight,  on  the 
amount  of  flour  employed  in  the  dough  batch)  was  used,  one-twentieth  of  that 
percentage,  by  weight,  of  hydrogenized  cottonseed  oil  having  a  melting-point  of 
57°  C.  may  be  used,  resulting,  it  is  claimed,  in  like  shortening  effects  with  the 
production  of  a  stiffer  and  springier  dough;  the  viscosity  of  the  dough  being 
maintained,  even  though  the  absorption  is  increased,  and  the  resultant  baked 
loaf  having  an  amount  of  moisture  sufficient  to  give  it  satisfactory  freshness  and 
flavor. 

Fats  of  a  melting-point  as  low  as  about  35°  C.  can  be  used  and  the  advantages 
incident  to  the  use  of  the  hard  fats  secured,  although  to  a  somewhat  lesser  degree 
than  when  the  shortening  agent  consists  of  the  higher  melting  fat  without  appre- 
ciable admixture  of  liquid  fat.  Even  when  fats  of  a  melting-point  as  low  as 
35°  C.  are  employed,  the  amount  of  the  shortening  agent  in  proportion  to  the 
flour  of  the  bread  is  but  a  fraction  of  the  amount  of  liquid  shortening  agent 
required  for  producing  the  same  shortening  effect  and  need  not  exceed  5  Ib.  of 
fat  to  880  Ib.  of  flour  and  bread.  Fats  of  higher  melting-point  require  a  cor- 
respondingly less  proportion  by  weight  of  fat  to  flour  to  produce  the  same 
shortening  effect,  and,  when  the  melting-point  of  the  fat  approximates  57°  C. 
the  amount  of  the  fat  may  be  diminished  to  say  2  Ib.  of  fat  to  880  Ib.  of  flour 
of  the  bread.  In  fact,  the  higher  the  melting-point  of  the  fat,  the  less  quantity, 
in  proportion  to  the  flour  employed,  will  be  required  to  obtain  a  baked  loaf  of 
satisfactory  shortness,  moisture-content  and  keeping  qualities. 

In  a  modification  of  the  process  of  making  a  shortening  composi- 
tion *  Kohman,  Godfrey  and  Ashe,  heat  flour  to  200°  C.  or  higher 
and  atomize  hydrogenated  oil  by  means  of  a  jet  of  air  into  the  flour. 
To  secure  this  admixture,  the  flour  is  sifted  in  at  the  top  of  a  cham- 
ber into  which  the  atomized  oil  is  being  introduced  and  on  coming 
in  contact  with  the  colder  particles  of  flour  the  hydrogenated  fat  is 
taken  up  by  the  flour.  The  latter  remains  in  pulverulent  condition 
after  cooling.  By  repeating  this  absorbing  operation  a  number  of 
times  upon  the  same  body  of  flour,  the  latter  will  take  up  from 
one-tenth  to  one-fifth  of  its  weight  of  the  fatty  material  and  yet 
remain  in  a  pulverulent  condition.  As  shortening  material,  this 
powder  may  be  admixed  with  the  requisite  amount  of  flour  and 
other  materials  used  in  making  bread,  thus  introducing  the  shorten- 
ing in  a  simple  manner. 

Hydrogenated  oil  in  the  form  of  a  powder  is  suggested  by  Alkin- 

*  U.  S.  Patent  No.  1,242,883,  and  1,242,884,  October  9,  1917. 


EDIBLE  HYDROGENATED   OILS  343 

son  *  as  a  shortener.  Corn  oil  is  hardened  to  a  melting-point  of  about 
148°  F.,  and  is  ground  in  a  mill  having  cooled  rolls  to  give  a  fine  powder. 
During  the  pulverization  the  temperature  of  the  fat  should  be  kept  below 
its  melting-point.  The  powder  is  stated  to  be  particularly  useful  as  a 
shortening  composition  for  cereal  baking  products  as  it  may  be  added 
to  the  flour  or  dough  in  definite  quantities  in  lieu  of  lard,  butter,  or  other 
solid  or  liquid  shortening  material  and  is  more  easily  mixed  with  flour 
and  dough  than  ordinary  shortening  fat  or  oil. 

An  edible  product  containing  hydrogenated  oil  and  carbohydrates 
in  the  form  of  a  powder  or  as  a  solid  cake  is  described  by  Ellis,  f 

A  shortening  and  leavening  composition  employing  hydrogenated 
oil  is  suggested  by  Holbrook  $  who  finds  it  possible  to  incorporate 
the  components  of  baking  powder  with  thickened  cottonseed  oil  to 
produce  a  composition  which  is  stated  to  be  stable  and  which,  when 
mixed  with  flour  and  water  to  form  dough,  will  serve  both  to  shorten 
and  leaven  the  mass. 

The  cottonseed  oil  is  thickened  to  the  desired  consistency  in  any  suitable 
manner,  but,  preferably,  by  partial  hydrogenation  or  by  mixing  it  with  from 
6  to  10  per  cent  of  hydrogenated  cottonseed  oil.  Such  a  fat,  it  is  asserted,  will 
not  become  rancid  and  does  not,  as  an  animal  fat  or  lard  appears  to  do,  more 
readily  acquire  rancidity  when  admixed  with  leavening  ingredients.  The  fat 
should  be  quite  free  from  water,  and  baking  powder  or  leavening  materials,  are 
intimately  mixed  therewith,  either  by  stirring  the  leavening  ingredients  into 
the  melted  fat  or  mixing  with  the  cold  solid  fat  in  a  mixing  machine.  The  fat 
and  leavening  materials  are  employed  in  such  proportions  that  when  the  prepara- 
tion is  mixed  with  about  eight  parts  by  weight  of  flour  and  with  sufficient  water 
or  milk  to  form  dough  and  the  mass  baked,  the  product  is  properly  shortened 
and  leavened.  Common  salt  for  seasoning  may  be  mixed  into  the  preparation 
so  that  the  baker  need  only  add  the  composition  to  flour  and  water  or  milk  to 
form  the  dough.  Since  the  baking  powder  is  embedded  in  the  body  of  lard-like 
fat  it  does  not  easily  absorb  moisture  from  the  air  and  hence  retains  its  gas- 
producing  capacity  indefinitely.  The  baking  results  attained  are  said  to  be 
superior  to  those  effected  by  separately  mixing  the  shortening  and  baking  powder 
in  the  dough  in  the  ordinary  manner.  The  explanation  offered  is  that  the 
baking  powder  ingredients  are  embedded  in  the  shortening  fat  and  the  develop- 
ment of  the  leavening  gas  is,  for  that  reason,  diminished  or  retarded  in  the  cold 
dough,  and  hence  more  of  the  leavening  action  occurs  when  the  dough  is  exposed 
to  the  heat  of  the  baking  oven.  For  this  reason  also,  the  preparation  is  consid- 
ered to  be  more  economical  since  by  its  use  a  smaller  amount  of  the  leavening 
agent  is  required.  Thus,  if  baking  soda  is  used  in  the  preparation  as  the  source 
of  the  leavening  gas,  the  amount  needed  to  properly  leaven  a  given  quantity 
of  flour  is  stated  to  be  about  25  per  cent  less  than  is  ordinarily  required,  and 
the  amount  of  baking  acid  required  to  react  with  the  soda  is  likewise  reduced. 

*U.  S.  Patent  No.  1,231,114,  June  26,  1917. 

fU.  S.  Patents  Nos.  1,276,507,  1,276,508  and  1,276,509,  August  20,  1918. 

t  U.  S.  Patent  No.  1,210,940,  January  2,  1917. 


344  THE  HYDROGENATION  OF  OILS 

The  leavening  ingredients  recommended  are  sodium  bicarbonate  and  finely-pul- 
verized acid  phosphate  such  as  mono-calcium  or  mono-sodium  phosphate.  Acid- 
phosphate,  particularly  mono-calcium  and  mono-sodium  phosphate,  are  inexpensive 
and  efficient  baking  acids,  but  they  absorb  atmospheric  moisture  and  must,  therefore, 
be  especially  prepared  for  use  in  ordinary  baking  powder.  Thus,  in  a  stable  baking 
powder,  mono-calcium  phosphate  should  be  used  in  granular  form  (i.e.,  such  that  it 
will  not  pass  through  a  156-mesh  sieve),  rather  than  in  pulverulent  form  (i.e.,  such 
as  would  pass  through  a  200-mesh  sieve).  But,  since  the  leavening  ingredients 
are  embedded  in  a  body  of  shortening  fat,  finely-pulverulent  acid  phosphates  can  be 
employed  in  Holbrook's  preparation  without  detriment  to  its  keeping  qualities 
and  with  advantage  in  the  baking  results  attained.  jLike  the  acid  phosphate,  the 
sodium  bicarbonate  and  salt  employed  may  be  finely  pulverized  and  dried. 

In  preparing  the  composition,  the  materials  and  proportions  by  weight  are, 
for  example,  as  follows: 

Thickened  cottonseed  oil 7  parts         Mono-calcium  phosphate ...   1 .25  parts 

Sodium  bicarbonate 1  part          Salt 1  part 

The  leavening  and  seasoning  ingredients  ar«  dried,  finely  pulverized  and  inti- 
mately mixed  with  the  thickened  cottonseed  oil  either  in  the  hot  or  cold  state. 
The  proportions  given  are  such  that  1  part  by  weight  of  the  improved  prepara- 
tion will  be  sufficient  to  properly  shorten  and  leaven  dough  containing  8  parts 
by  weight  of  flour,  which  is  stated  to  be  the  proportion  in  which  common  animal 
shortening  fat  or  lard  is  generally  used. 

Burchanal  *  prepares  a  food  compound  closely  simulating  lard  in 

its  physical  and  chemical  characteristics,   consisting  of  a  mixture  of 

an  oil  and  a  hardening  agent  produced  by  hydrogenizing  an  oil  or 
liquid  fat. 

In  its  most  desirable  form,  the  product  is  a  vegetable  one,  consisting  of  a 
mixture  of  about  85  per  cent  of  cottonseed  oil  and  15  per  cent  of  hydrogenized 
cottonseed  oil.  In  the  manufacture  of  this  product,  oil  is  hydrogenized,  by  vig- 
orous agitation  in  a  closed  vessel  containing  an  atmosphere  of  compressed  hydro- 
gen, a  catalytic  agent,  such  as  kieselguhr  impregnated  with  finely-divided  nickel, 
being  maintained  in  suspension  in  the  oil  and  the  charge  being  heated  to  a  tem- 
perature of  about  155°  C.  The  oil  is  thereby  converted  into  a  white  or  yellowish 
solid,  containing  additional  hydrogen  about  5  to  6  per  cent  more  than  in  the 
nonhydrogenized  material,  having  a  saponification  value  of  about  190,  an  iodine 
value  of  about  20,  a  melting-point  of  about  56°  C.,  and  a  titre  of  about  55°  C., 
giving  no  reaction  for  cottonseed  oil  under  the  Halphen  test.  Suitable  propor- 
tions of  the  hydrogenized  and  hardened  oil  and  of  the  non-hydrogenized  oil 
are  now  thoroughly  mixed  or  blended.  In  case  about  15  per  cent  of  hydro- 
genized cottonseed  oil  and  85  per  cent  of  non-hydrogenized  cottonseed  oil  are 
thus  mixed,  the  final  product  is  stated  to  be  a  '.vhite  or  yellowish  semi-solid, 
having  a  saponification  value  of  about  195;  an  iodine  value  of  about  95;  a 
melting-point  of  about  42°  C.;  and  a  titre  of  about  36°  C. 

In  case  a  harder  hydrogenized  stock  is  used,  its  proportion  may  be  corre- 
spondingly reduced.  For  example,  if  the  oil  used  for  hardening  is  hydrogenized 

*U.  S.  Patent  No.  1,135,935,  April  13,  1915. 


EDIBLE  HYDROGENATED  OILS  345 

to  an  iodine  value  of  8  or  9,  approximately  10  per  cent  of  the  hardened  material 
are  stated  to  be  required  to  yield  a  mixture  having  physical  constants  approxi- 
mately as  above  specified. 

Burchanal  *  produces  an  incompletely  hydrogenated  lard-like  fat 
from  cottonseed  oil,  with  the  stated  object  of  providing  a  new  food 
for  a  shortening  in  cooking,  in  which  the  liability  to  become  rancid 
is  minimized,  and  in  which  the  components  of  such  vegetable  oils 
which  are  inferior  and  detrimental  to  use  as  such  a  food  product 
have  been,  to  a  large  extent,  converted  into  a  higher  and  more 
wholesome  form. 

All  such  vegetable  oils  contain  glycerides  of  unsaturated  fatty  acids,  and 
among  these,  notable  quantities  of  fatty  glycerides  of  lower  saturation  than 
olein.  Oxidation  is  largely  the  cause  of  rancidity,  which  oxidation  weakens 
the  fat  at  the  point  of  absorption  at  the  double  bonds,  and  these  glycerides  of 
lesser  saturation  readily  absorb  oxygen  from  the  air  at  ordinary  temperatures, 
while  the  more  highly  saturated  glycerides,  as  olein,  only  absorb  oxygen  at 
elevated  temperatures.  It  is  evident,  'Burchanal  observes,  that  oils  or  fats  con- 
taining notable  quantities  of  glycerides  of  linolic  acid,  or  of  lesser  saturation,  are 
distinctly  inferior  as  an  edible  product  to  those  containing  a  minimum  of  these 
glycerides  with  a  larger  per  cent  of  olein.  On  the  other  hand,  while  it  is  im- 
portant to  get  rid  of  the  readily  oxidizable  glycerides  of  lower  saturation  it  is 
also  important  not  to  supply  too  large  a  per  cent  of  fully  saturated  glycerides. 
The  saturated  glycerides  of  the  arachidic,  stearic,  palmitic  and  other  groups 
are  stated  to  be  of  very  small  value  for  shortening,  inasmuch  as  it  is  the  liquid 
fats  which  contribute  this  value  to  the  material.  Saturated  fats,  however,  serve 
the  purpose  of  congealing  the  shortening  within  the  food,  and  thus  retain  it 
equally  distributed  throughout  the  whole.  Oil,  liquid  at  the  ordinary  tempera- 
tures is  not  regarded  as  making  the  best  shortening,  because  the  oil  remains 
liquid,  keeping  the  food  in  a  soggy  condition,  and  the  oil  will  even  settle  to 
the  under  part  of  the  cooked  product.  Moreover,  fats  of  a  melting-point  above 
the  temperature  of  the  human  body,  98°  F.,  are  not  so  digestible  as  fats  which 
are  liquid  at  this  point,  or  which  have  a  melting-point  below  98°  F.  Burchenal 
therefore  endeavors  to  change  the  chemical  composition  of  the  oil  (cottonseed)  to 
obtain  a  product  with  a  high  percentage  of  olein,  a  low  percentage  of  linolin  and 
the  lesser  saturated  fats,  and  with  only  sufficient  stearine  to  make  the  product 
congeal  at  ordinary  temperatures. 

Hydrogenation  is,  therefore,  stopped  when  the  oil  has  been  converted  into  a 
product  which  cools  to  a  white  or  yellowish  semi-solid  resembling  lard.  In 
many  respects,  it  is  claimed,  the  product  is  superior  to  the  best  leaf  lard  as  a 
shortening.  It  is  not  so  liable  to  become  rancid  and  the  product  can  be  heated 
to  a  considerably  higher  temperature  than  lard  without  smoking  or  burning. 
The  high  temperature  to  which  the  product  can  be  raised  without  smoking  or 
burning  is  stated  to  make  the  product  ideal  for  frying  as  a  crust  forms  almost 
instantly  on  the  food  fried,  which  prevents  any  absorption  of  the  shortening. 
Burchanal  gives  data  on  the  analytical  constants  of  the  product.  A  lard-like 
product  thus  prepared  from  cottonseed  oil  has  a  saponification  value  of  about 

*  U.  S.  Patent  No.  1,135,351,  April  13,  1915. 


346  THE  HYDROGENATION  OF  OILS 

195;  and  an  iodine  value  ranging  from  about  55  to  about  80.  The  product 
having  an  iodine  number  of  55  has  a  titre  of  about  42°  and  a  melting-point  of 
about  40°  C.;  that  having  an  iodine  value  of  80  has  a  titre  of  about  35°  and 
a  melting-point  of  about  33°  C.  While  but  partially  hydrogenized,  containing 
from  about  1.5  per  cent  to  2.5  per  cent  of  additional  hydrogen  more  than  in 
the  non-hydrogenized  material,  it  shows  no  free  cottonseed  oil  when  subjected 
to  the  Halphen  test.  It  contains  from  20  to  25  per  cent  of  the  fully  saturated 
glycerides,  from  5  to  10  per  cent  linolin  and  from  65  to  75  per  cent  olein,  and 
an  average  of  a  number  of  samples  gives  23  per  cent  of  saturated  fats,  7.5  per 
cent  linolin  and  69.5  per  cent  olein,  while  the  cottonseed  oil  before  treatment 
contained  37  per  cent  linolin  and  46  per  cent  olein. 

Walker  *  proposes  a  method  of  making  fatty  food  products  which 
consist  in  partially  hydrogenating  unsaturated  compounds  of  vege- 
table or  animal  oils  and  fats,  by  any  method  and  arresting  the 
operation  at  a  predetermined  point  short  of  saturation  and  where 
the  consistency  of  the  product  is  above  or  below  that  of  a  given  oil 
or  fatt^f  body,  and  then  incorporating  with  the  partially  hydro- 
genated  body  an  unhydrogenated  oil  or  fatty  body  to  produce  a 
product  of  the  desired  consistency  and  having  the  characteristic 
flavor  desired.  For  example,  purified  cottonseed  oil  is  hydrogenated 
until  the  action  reaches  a  point  where  the  stearine  produced  amounts 
to  about  22  per  cent  of  the  oil  treated,  there  remaining  about  80 
per  cent  of  unsaturated  oil.  These  proportions  may  vary  with  wide 
limits,  depending  on  the  consistency  of  the  final  product  desired 
and  the  nature  of  the  subsequent  additions.  To  the  hydrogenated 
product  freed  from  catalyzer,  oily  lard  is  added,  preferably  by 
means  of  incorporating  rolls,  the  quantity  being  sufficient  to  give 
to  the  hydrogenated  product  a  lard  consistency. 

The  process  is  stated  to  be  equally  applicable  to  making  butter 
substitutes,  the  manufacture  of  coatings  for  chocolate  creams,  con- 
fections and  the  like. 

Walker  considers  it  is  important  that  the  hydrogenating  action  be 
carried  to  a  point  affording  a  consistency  above  or  below  that  of 
the  final  product,  and  then  to  secure  the  desired  consistency  by 
incorporation  of  a  suitable  oil  or  solid  fatty  body,  thereby  securing 
the  benefits  of  the  added  body  as  a  hardening  or  softening  agent 
while  retaining  its  desirable  flavoring  characteristics  unimpaired. 
In  general,  the  hydrogenating  action  may  vary  between  a  product 
which  is  soft  and  greasy  to  a  solid,  but  for  the  preparation  of  lard 
and  butter  substitutes  the  hydrogenating  action  should  afford  a 
product  containing  about  18  to  22  per  cent  of  stearine. 

*  U.  S.  Patent  No.  1,206,954,  December  5,  1916. 


EDIBLE  HYDROGENATED  OILS  347 

At  the  Institute  of  Hygiene  in  Wurzburg,  the  Director,  K.  B. 
Lehmann  has  busied  himself  with  the  question  of  the  edibility  of 
hardened  oil  *  and  in  particular  to  answer  the  questions:  (1)  In  the 
hardening  process  does  the  fat  take  up  quantities  of  nickel  which 
would  be  injurious?  (2)  Does  the  product  exhibit  any  abnormal 
characteristics  as  viewed  from  the  chemical  standpoint?  and  (3)  How 
well  fitted  is  the  hardened  fat  for  human  consumption  as  evidenced 
by  the  effects  produced  by  it  on  animals  and  on  men  when  taken  as 
an  article  of  diet? 

An  analysis  of  several  samples  of  hardened  oils  showed  that  nickel  was  present 
in  amounts  ranging  from  0.1  milligram  to  6  milligrams  per  kilogram  of  fat.  In 
cottonseed  oil,  for  example  the  amount  of  nickel  present  was  about  0.5  milli- 
gram per  kilo.  This  means  that  in  2,000,000  parts  of  the  fat,  but  one  part  of 
nickel  is  present.  Lehmann  has  shown  that  food  prepared  in  nickel  vessels 
contains  from  11  to  64  milligrams  of  nickel  per  kilo  and  that  by  the  use  of  such 
nickel  vessels  in  the  preparation  of  foodstuffs  as  much  as  117  milligrams  of  nickel 
may  be  consumed  in  a  day's  ration.  In  a  series  of  tests  made  with  animals, 
from  6  to  10  milligrams  of  nickel  per  kilogram  body  weight  of  the  animal,  were 
fed  for  a  period  of  200  days  without  injurious  effects.  In  tests  made  on  man, 
up  to  1  to  2  milligrams  of  nickel  per  kilogram  body  weight  were  consumed 
without  injury.  No  case  has  been  reported  of  acute  or  chronic  nickel  poisoning 
due  to  the  general  use  of  nickel  vessels  in  the  household  for  the  preparation  of 
food.  Assuming  the  extreme  case  of  a  consumption  of  100  g.  per  day  of  hard- 
ened fat,  the  content  of  nickel. in  this  amount  of  fat  would  be  0.6  of  a  milli- 
gram when  taking  the  fat  having  the  maximum  per  cent  of  nickel.  Under 
ordinary  conditions  the  amount  of  nickel  would  be  about  0.1  of  a  milligram  per 
day,  which,  in  comparison  with  the  possibility  of  consuming  over  100  milligrams 
of  nickel  per  day  in  food  cooked  in  nickel-coated  vessels,  is  indeed  a  wholly 
insignificant  amount. 

A  chemical  examination  of  the  hardened  fat  (prepared  from  peanut,  sesame 
and  cottonseed  oil)  did  not  disclose  anything  prejudicial  from  the  hygienic 
standpoint. 

After  having  secured  these  results  from  the  ingestion  of  nickel  and  rinding 
that  no  injurious  effects  were  detectable  when  nickel  in  vastly  larger  amounts 
than  found  in  hardened  fat  was  daily  consumed,  Lehmann  directed  his  atten- 
tion to  the  continued  action  of  the  hardened  fat  itself,  first  on  animals  and  then 
on  man. 

For  a  period  of  five  months,  50  g.  of  the  fat  were  daily  fed  to  dogs  of  body 
weight  4  to  8  kilograms  and  the  suitability  of  the  fat  as  a  foodstuff  determined 
from  this  standpoint.  The  results  were  entirely  favorable.  Lehmann  then 
began  a  series  of  tests  of  the  fat  on  members  of  his  own  and  other  families.  In 
three  families  7  Ib.  of  hardened  fat  per  month  were  used  over  a  period  of  sev- 
eral months  duration  without  any  ill  results.  In  his  own  family  the  product 
has  been  used  regularly  for  six  months  and  no  criticism  can  be  found  against 
the  fat.  In  summarizing  his  work,  Lehmann  concludes  from  theoretical  and 
practical  investigations  that  hardened  fat  is  a  most  rational  and  desirable  fatty 

*  Chem.  Ztg.,  1914.  798. 


348  THE  HYDROGENATION  OF  OILS 

food   and   regards   it  as  a   most   valuable  material  to  use  in   the   production   of 
oleomargarine. 

Vuk  offers,*  as  a  partial  explanation  of  the  divergent  views  of 
various  authorities  concerning  the  harmful  effects  arising  from  the 
use  of  nickel  utensils  for  cooking  and  containing  foods,  certain 
results  showing  that  various  forms  of  nickel  are  dissolved  by  dilute 
acids  with  different  degrees  of  facility. 

By  heating  separate  portions  of  700  cc.  of  5  per  cent  acetic  acid  for  2|  hours 
on  a  water-bath  together  with  each  of  the  different  kinds  of  nickel  of  which 
exactly  16,800  sq.  mm.  were  exposed  to  the  action  of  the  acid  in  each  case, 
the  following  amounts  of  nickel  were  found  to  have  been  dissolved,  results 
being  expressed  in  mg.  of  nickel  per  sq.  dm.  of  surface:  Rolled  15.5-16.9,  case 
25.5-28.8,  electrolytic  30.6-30.8,  drawn  33.1-39.0,  and  Berndorf  "  Rein  Nickel  " 
61.4-65.4. 

As  regards  the  use  of  nickelware  in  the  preparation  of  food 
Gheorghiu  f  boiled  ordinary  salt  pickles  and  meat  with  water  and 
salt  two  hours  in  a  nickel  dish,  the  resulting  products  (pickles,  liquid, 
fat  and  meat)  were  examined  for  metal  with  the  following  results: 
pickles  107.4  mg:,  juice  135.6  mg.,  fat  16  mg.,  and  meat  0.0  mg. 
per  kg.  substance. 

An  edible  product  comprising  edible  fatty  hydrogenated  material 
free  from  catalytic  metal  is  mentioned  in  U.  S.  Patent  to  Ellis 
No.  1,097,308,  May  19,  1914. 

A  method  of  increasing  the  glycerine  content  of  oils  and  fats  is  recommended 
by  Naamlooze  Vennootschap  Ant.  Jurgens  Vereenigde  Fabrieken  J  which  consists 
in  heating  the  fatty  material  with  glycerine  in  the  presence  of  a  finely-divided 
metal  oxide,  such  as  alumina,  thoria  or  titanium  oxide.  It  is  supposed  that 
bodies  of  this  character  exert  a  catalytic  action  under  these  conditions.  By 
the  treatment,  the  triglyceride  is  converted  to  a  greater  or  less  degree  into  mono- 
or  diglyceride.  Glycerine  enrichment  has  been  found  to  improve  the  flavor  of 
many  oils,  such  as  cod  liver  and  castor  oil. 

From  cottonseed  oil  a  product  containing  a  considerable  proportion  of  digly- 
ceride was  prepared  as  follows: 

One  hundred  parts  cottonseed  oil,  10  parts  glycerine  and  3  parts  alumina  were 
heated  for  one  hour  at  250°  in  an  enamelled  receptacle  fitted  with  a  mechanical 
stirrer.  To  avoid  oxidation  a  slow  current  of  hydrogen  was  passed  through  the 
apparatus.  At  the  end  of  three  hours  the  excess  of  glycerine  was  removed  by 
washing  with  water. 

Before  such  treatment,  the  oil  exhibited  a  saponification  value  of  189  corre- 
sponding to  a  glycerine  content  of  10.3  per  cent.  The  acetyl  number  was  12. 
After  the  treatment,  a  portion  of  the  oil  was  acetylated  and  1  g.  of  the  acety- 
lated  product  was  saponified,  calling  for  263.5  milligram  potassium  hydrate. 

*  Z.  Nahr.-Genussm.  28,  103^   1914;   Chem.  Abs.,  1915,  109. 

f  Ber.  pharm.  Ges.,  24,  303,  1914;  Chem.  Abs.,  1915,  487. 

J  Seifen.  Ztg.,  1914,  1092;  German  Patent  No.  277,641,  May  26,  1914. 


EDIBLE  HYDROGENATED  OILS  349 

From  this  is  deducted  the  acetyl  value  found,  leaving  251.5  milligrams  potassium 
hydrate,  corresponding  to  the  total  hydroxyl  groups  of  the  glycerine  present. 
This  is  equivalent  to  13.75  per  cent  of  glycerine  or  3.45  per  cent  more  than  was 
present  in  the  original  oil.  If  calculated  to  diglyceride,  the  content  of  the 
latter  would  amount  to  66  per  cent.  In  another  test,  100  parts  sesame  oil, 
12  parts  glycerine  and  10  parts  comminuted  kieselguhr  were  heated  to  230° 
under  conditions  similar  to  those  employed  with  the  cotton  oil.  After  heating 
for  three  hours,  the  product  was  cooled  and  washed  with  warm  water. 

Saponification  value  of  the  original  oil 191.2 

Glycerine  content  corresponding 10 . 5 

Acetyl  number 11.5 

After  treatment  and  acetylation  1  g.  oil  required..  .  259.9  mg.  KOH 
Deducting  acetyl  number 11.5 


284.4 

This  result  corresponds  to  a  glycerine  content  of  13.59  per  cent  equivalent 
to  60  per  cent  diglyceride. 

It  is  stated  that  the  formation  of  glyceride  by  heating  fatty  acids  and  gly- 
cerine is  already  known  as  also  the  fact  that  mono-  or  diglycerides  form  on 
heating  a  triglyceride  with  glycerine.  The  use  of  a  contact  body  to  enable  the 
reaction  on  triglycerides  to  be  effected  expeditiously  at  temperatures  between 
200°  to  250°  is  the  indicated  improvement. 

A  pamphlet  entitled  "The  Present  and  Future  Peril  to  Our  Com- 
merce and  Industry,"  by  Dr.  Hugo  Schweitzer,  discusses  the  devel- 
opment of  methods  of  converting  waste  into  edible  fats.  Schweitzer 
states:  "  Germany  imported  from  us  (U.  S.)  altogether  $23,000,000 
worth  of  fats,  principally  lard,  for  culinary  purposes.  The  inter- 
ference with  our  seaborne  commerce  through  the  action  of  the  British 
Navy  has  suspended  our  trade  with  Germany  in  this  commodity." 

"  Fortunately  for  Germany,  but  unfortunately  for  us,  a  modern  development 
in  the  fat  and  oil  industry  has  provided  her  with  means  to  utilize  materials  which 
hitherto  were  unfit  to  eat. 

"  By  the  so-called  method  of  hardening  fats  and  oils — that  is,  by  treating 
them  with  hydrogen — they  are  not  only  converted  from  the  cheaper  liquid 
into  the  higher-priced  solid  form,  but  their  taste  and  odor  are  so  improved  that 
they  might  serve  for  culinary  purposes,  while  without  being  subjected  to  the 
hardening  process,  they  could  not  possibly  be  thus  employed.  Even  the  various 
grades  of  fish  oil  can  thus  be  rendered  available  as  food  materials.  Germany 
cannot  possibly  be  cut  off  from  the  supply  of  these  oils.  The  fisheries  of  the 
Baltic  and  the  North  Sea,  of  Norway  and  Sweden  would  place  an  inexhaustible 
and  cheap  source  of  fats  and  oils  at  the  disposal  of  the  German  people,  to  whom 
an  opportunity  is  thus  afforded  to  remain  forever  independent  of  the  import  of 
edible  fats  from  the  United  States. 

"  By  this  hardening  process  even  the  waste  fats  (foots)  obtained  in  refining 
can  be  utilized  not  only  for  soap  making,  but  also  for  foodstuffs.  In  short,  by 


350  THE  HYDROGENATION  OF  OILS 

suitable  treatment  with  hydrogen,  all  oleaginous  matter  may  be  converted  into 
edible  substances."  * 

UTILIZATION  OF  FISH  OIL 

It  is  reported  by  J.  Ind.  &  Eng.  Chem.  (1918,  487)  that  authorities  in  Germany 
have  prohibited  the  supply  of  herrings  to  the  trade  except  with  the  heads  removed 
in  order  that  these  may  be  utilized  for  the  production  of  oil,  albumen  and  phos- 
phate of  lime.  Fish  offal  is  now  utilized  in  Germany  to  produce  food  for  human 
beings  as  well  as  for  animals.  Offal  collected  from  fish  preserving  factories,  res- 
taurants, etc.,  is  dried  and,  after  the  extraction  of  the  oil,  ground.  The  meal  so 
obtained  frequently  contains  50  per  cent  and  upwards  of  albumen  and  phosphate  of 
lime,  the  latter  being  obtained  from  the  bones  and  heads.  By  chemical  methods, 
the  albumen  is  extracted  from  the  fish  meal  and  rendered  available  for  human 
consumption.  From  the  oil  phosphate  of  lime  for  animal  fodder  is  obtained  by 
means  of  benzine,  benzol,  and  other  fat  solvents.  The  oil  is  also  used  for  various 
technical  purposes.  Specially  good  kinds  can  be  hardened  by  hydrogenation  and 
rendered  suitable  for  production  of  eatable  fat.  The  hardened  fat  looks  like  tallow 
and  is  almost  odorless. f 

After  determining  that  corn  oil  is  an  economic  substitute  for  olive 
oil,  Dean  L.  E.  Sayre,  of  the  Kansas  University  School  of  Pharmacy, 
Lawrence,  Kan.,  is  reported  by  the  Soap  Gazette  &  Perfumer 
(1915,  99)  to  be  experimenting  to  determine  whether  it  is  a  satis- 
factory substitute  for  lard.  Some  of  the  liquid  oil,  which  is  heavy 
and  brown,  was  hydrogenated.  In  this  condition  it  appeared  white 
and  about  the  consistency  of  cocoa  butter,  and  melted  at  the  tem- 
perature of  beeswax.  Dean  Sayre  believes  that  the  hydrogenated 
oil  can  be  used  in  place  of  lard,  the  dietetic  value  of  the  oil  being 
claimed  to  be  as  great  as  that  of  either  olive  oil  or  cottonseed  oil. 
The  patented  frying  mediums  are  stated  to  be  hydrogenated  cotton- 
seed oil.J 

The  Proctor  &  Gamble  Company  have  erected,  at  Hamilton,  Ontario,  a  plant 
for  the  manufacture  of  Crisco,  and  will  also  operate  glycerine  and  cottonseed 
oil  refineries  for  their  Canadian  trade.  The  Crisco  building  is  similar  in  con- 
struction to  their  Ivorydale  factory,  the  inner  walls  being  of  white  glazed  brick, 
the  air  "circulation  undergoing  a  constant  process  of  purification.  § 

A  method  of  purifying  hydrogenated  fats  is  described  by  Joslin.lf 

It  is  stated  that  hydrogenated  fats  contain  fatty  acids  and  other  bodies  which 
effect  the  taste  and  odor  and  also  certain  readily  oxidizable  components  which 
may  be  removed  by  treatment  with  denatured  alcohol  or  wood  spirits.  A 
volume  of  alcohol  approximately  equal  to  the  volume  of  the  fat  taken  is  agitated 

*  From  an  address  delivered  before  the  German  University  League,  New  York  City, 
February  3,  1915. 

t  Leimdorfer  refers  to  the  fat-hardening  process  in  connection  with  the  edible  field. 
Seifen.  Ztg.,  1915,  344. 

J  See  also  Lackey  and  Sayre,  J.  Am.  Pharm.  Assoc.  6,  348. 

§  Amer.  Perfumer,  1915,  104;  Soap  Gazette,  1915,  224. 

1  U.  S.  Patent  No.  1,152,023,  August  31,  1915. 


EDIBLE  HYDROGENATED  OILS 


351 


with  the  latter  while  maintaining  (he  mixture  in  a  fluid  condition.  As  low  a. 
temperature  as  is  possible  is  employed,  in  fact,  just  sufficient  to  maintain  the 
proper  degree  of  fluidity  of  the  fat.  A  small  amount  of  alcohol,  ordinarily  from 
3  to  5  per  cent,  dissolves  in  the  fat  while  the  impurities  and  objectionable  sub- 
stances dissolve  in  the  alcohol.  The  alcohol  with  the  dissolved  substances  is 
removed  by  decantation  and  the  alcohol  taken  up  by  the  fat  is  removed  by  dis- 
tillation. This  step  is  preferably  followed  by  a  further  treatment  consisting  in 
passing  steam  or  inert  gas  through  the  fat.  The  refined  substance  is  allowed  to 
cool  in  an  atmosphere  in  inert  gas.  In  some  cases  more  than  one  treatment 
with  alcohol  may  be  required  to  secure  the  required  degree  of  purification. 
The  purified  hydrogenated  fat  is  stated  to  be  characterized  by  containing  a 
relatively  inappreciable  proportion  of  free  fatty  acids  and  a  relatively  large  pro- 
portion of  combined  fatty  acids,  and  by  being  free  from  impurities,  unsaponifiable 
bodies,  rancidity-tending  oxidized  products  or  other  bodies  of  an  unstable  nature. 

For  refining  hydrogenated  fats  to   produce  edible  products,  Wil- 
buschewitsch  *  removes  the  fatty  acids  by  saponification  successively 


FIG.  54a. 

with  carbonate  of  soda  and  caustic  soda,  subsequently  removing 
the  soap  and  washing  the  oil  thoroughly,  then  deodorizing  with 
superheated  steam  in  a  vacuum  apparatus.  Fig.  54a  illustrates 
apparatus  in  which  the  oil  and  alkali  are  mixed  by  a  circulating  pump. 

A  statement  by  Oelwerke  Germania  in  Seifensieder  Zeitung,  1914,  208,  regard- 
ing the  Leprince  and  Siveke  patent  of  1902  is  as  follows: 

Hence  it  follows  as  a  matter  of  fact  that  the  process  of  German  Patent  No. 

*  U.  S.  Patent  No.  1,177,911,  April  4,  1916. 


352  THE  HYDROGENATION  OF  OILS 

141,029  made  a  new  path  in  the  industry  and  first  solved  the  important  problem 
of  oil  hardening.  No  one  before  this  had  thought  of  the  possibility  of  making  a 
solid  edible  fat  from  oils.  This  information  is  first  supplied  by  Patent  No.  141,029. 

The  properties  and  uses  of  various  hardened  oils  are  referred  to 
by  Thompson,*  who  states  his  impressions  of  the  industry  as  viewed 
in  1914.  A  comparison  of  conditions  at  that  time  with  those  pre- 
vailing since  the  present  world  war  began  is  interesting. 

The  total  cost  of  the  hardening  operation  differs  widely  in  different  places,  and 
varies  some  with  the  degree  of  hardness  to  be  produced.  It  is  said  to  average 
around  1  cent  per  pound.  In  some  places  it  has  been  done  for  a  commerical  toll 
of  If  cents,  which  presumably  leaves  a  profit. 

The  combined  capacity  of  the  hydrogenating  plants  of  Europe  is  estimated 
for  1914  at  250,000  tons  (1,375,000  barrels),  which  is  two  or  three  times  as  much 
as  has  ever  been  treated.  These  plants  are  in  England,  Norway,  Germany 
and  France,  and  are  engaged  at  present  chiefly  on  fats  for  soap  and  candles. 
They  are  hardening  linseed,  whale,  soya  bean  and  cottonseed  oils. 

The  great  increase  in  the  demand  for  margarin  in  Europe,  for  compDund 
lard  in  the  United  States  and  for  hard  soap  all  over  the  civilized  world  has 
resulted  in  closely  crowding  the  supply  of  natural  hard  fats,  while  liquid  oils 
are  relatively  abundant.  A  few  years  ago  strictly  edible  liquid  oils  seemed  to 
be  growing  scarcer,  but  the  new  scheme  of  deodorization  began  to  relieve  this 
shortage  by  lifting  the  so-called  soap  oils  into  the  edible  class.  The  same 
process  was  applied  to  copra  and  palm-kernel  oils,  and  finally  caused  a  scarcity 
of  soap  greases.  Hydrogenation  now  promises  a  further  readjustment  of  con- 
ditions by  permitting  the  transfer  at  will  of  any  oil  from  the  liquid  to  the 
solid  class,  and  it  will  bring  into  use  some  relatively  rare  oils  and  encourage 
the  production  of  still  others. 

LINSEED  OIL.     (THOMPSON) 

Linseed  oil,  in  1914,  offered  the  greatest  attraction  to  hardeners.  The  price 
in  Liverpool  in  April,  1914,  was  5.40  cents  per  pound,  or  2  cents  cheaper  than 
average  tallow.  It  is  now  successfully  hardened  and  used  for  soap  on  a  large 
scale,  750,000  barrels  being  the  trade  prediction  for  1914. 

The  world's  crop  of  linseed  varies  greatly  from  year  to  year.  In  1913  there 
was  a  record  crop  of  about  2,700,009  metric  tons,  or  half  a  million  above  that  of 
the  year  before.  Omitting  the  crush  of  Russia,  which  is  about  350,000  tons  out 
of  a  crop  of  500,000,  Europe  crushed  linseed  in  the  last  two  years  as  follows: 

1912.  1913. 

Metric  Tons.     Metric  Tons. 

Germany 324,700  560,000 

United  Kingdom 290,000  665,400 

Netherlands 156,600  207,600 

Others 235,000  266,700 


Totals 1,006,300      1,700,000 

Oil  made  (estimated  30  per  cent) .  .  .      301,890    ,     510,000 

Equivalent,  barrels 1,660,000      2,805,000 

*  Special  Agents  Series,  Bureau  of  Foreign  and  Domestic  Commerce;     Oil,  Paint  and 
Drug  Reporter,  October  19,  1914,  36. 


EDIBLE  HYDROGENATED  OILS  353 

Seventy  per  cent,  increase  in  the  oil  supply  had  a  depressing  influence  on  the 
market  and  caused  the  price  to  decline  through  the  year  in  the  face  of  a  general 
advance  for  other  fats.  This  fact  no  doubt  had  its  weight  in  accelerating  the 
development  of  hardening  plants.  The  crop  for  1914  is  expected  to  be  smaller, 
about  like  that  of  1912;  and  if  so,  this  extra  demand,  together  with  the  growing 
demand  from  the  linoleum  industry,  will  tend  to  advance  prices. 

FISH  OILS.     (THOMPSON) 

Fish  oils  (whale,  seal,  menhaden,  sardine,  etc.),  have  generally  ruled  lower  in 
price  than  vegetable  oils,  because  of  their  restricted  uses.  They  have  not  been 
successfully  used  in  the  manufacture  of  soap  because  of  the  persistent  smell. 
It  is  claimed  that  the  new  hardening  process  eliminates  all  trace  of  smell  and 
taste  and  renders  these  oils  as  useful  and  valuable  as  tallow  for  soap.  It  is 
even  claimed  that  they  may  be  used  in  margarine.  Whale  oil  has  advanced  a 
cent  or  two  per  pound  on  this  news,  but  is  still  only  about  5  cents  against  7 
to  8  for  tallow.  One  large  hardening  plant  has  already  been  established  in 
Norway  (De  Nordske  Fabrik  Fredrikstad),  principally  for  treating  whale  oil, 
and  another  plant  is  also  being  built.  The  combined  capacity  of  these  two  plants 
is  estimated  at  550,000  barrels  for  1914.  Other  plants  in  Germany  and  England 
are  also  working  on  fish  oils.  This  has  greatly  stimulated  the  whaling  indus- 
try, 800,000  barrels  being  estimated  as  the  catch  for  1913,  which  is  many  times 
greater  than  any  previous  year.  Although  new  whaling  fields  are  continually 
being  exploited,  extinction  of  the  species  is  predicted  if  the  present  activity 
continues. 

Oils  are  being  extracted  in  relatively  small  quantities  at  various  fishing  cen- 
ters in  England,  Japan,  South  Africa  and  other  countries.  When  there  hap- 
pens to  be  a  surplus  catch  beyond  the  capacity  of  the  local  market  they  are 
worked  for  oil  instead  of,  as  formerly,  being  thrown  out  on  the  land  or  worked 
whole  into  commercial  fertilizers.  The  introduction  of  steam  trawlers  in  Eng- 
land has  enlarged  the  fishing  radius  with  a  consequent  increase  of  catch.  The 
new  outlet  for  fish  oil  will  help  to  absorb  the  surplus  and  prevent  an  economic 
waste. 

SOYA  BEAN  OIL.     (THOMPSON) 

From  the  present  crop  of  two  or  two  and  a  half  million  tons  of  soya  beans 
could  be  made  two  million  barrels  of  oil,  but  no  such  amount  is  being  made, 
or  at  least  offered  to  commerce.  Only  200,000  to  250,000  barrels  are  made  in 
Europe,  and  any  amount  greatly  in  excess  of  this  would  have  to  move  as  oil 
from  China  and  Japan.  As  this  oil  is  now  definitely  moving  in  the  direction  of 
salad,  and  as  that  trade  must  draw  a  supply  from  somewhere,  the  probabilities 
are  that  in  the  en- 1  it  will  be  allowed  to  go  that  way  and  not  much  of  it  be 
intercepted  for  hardening. 

PEANUT  AND  COTTONSEED  OILS.     (THOMPSON) 

Peanut  oil  is  so  much  esteemed  in  liquid  form  for  salad  and  for  margarin  that 
there  will  not  be  so  much  margin  of  profit  in  hardening  it  as  for  some  of  the 
others,  and  it  will  probably  be  left  for  exploitation  at  a  later  date. 

Oil  from  Egyptian  cottonseed,  say  374,000  barrels  made  in  Germany  and 
England,  is  all  tending  toward  the  edible  trade,  though  about  half  of  it,  natural 
or  hardened,  still  goes  into  soap.  Eventually  most  of  it  will  probably  go  into 


354  THE  HYDROGENATION  OF  OILS 

compound  lard  and  margarin,  perhaps  in  the  hardened  state,  especially  as  it  is 
claimed  that  the  hardening  process  also  deodorizes. 

Oil  from  American  decorticated  cottonseed,  three  to  three  and  a  half  million 
barrels,  is  now  practically  all  turned  to  edible  uses,  and  its  value  will  be  much 
enhanced  by  the  new  discovery.  Either  hardened  in  the  United  States  or  shipped 
abroad  to  be  hardened  for  margarin  and  compound  lard,  it  becomes  an  imme- 
diate competitor  of  copra  oil,  the  highest-priced  ingredient  on  the  market. 
American  oil  will  always  have  the  preference,  because  it  exists  in  the  largest 
amount,  thus  presenting  the  largest  possibility  for  selecting  a  uniform  supply. 
Reversing  the  usual  order,  increased  domestic  demand  for  the  new  form  will 
absorb  such  quantities  that  export  prices  may  be  maintained  at  high  levels. 

Thompson  *  observes  that  formerly  artificial  lard  was  made  by  the  admixture 
of  bleached  liquid  cottonseed  oil  with  oleo  stock  or  refined  tallow  in  the  right  pro- 
portion to  give  a  consistency  as  nearly  like  lard  as  possible.  But  since  the  intro- 
duction of  the  hardening  process,  much  of  the  artificial  lard  is  made  by  mixing 
liquid  oil  with  hardened  cottonseed  oil.  Margarine,  or  artificial  butter  is  in  general 
compounded  from  the  same  kind  of  fats  as  used  for  artificial  lard.  Natural  hard 
fats  are  more  difficult  to  obtain  and  higher  in  price  than  liquid  oils,  so  the  arti- 
ficially hardened  fats  have  become  immensely  popular  for  all  these  mixtures,  even 
whale  oil  having  been  used  during  the  war. 

A  liquid  hydrogenated  oil  food  product  is  described  by  Lowen- 
stein  f  which  is  stated  to  be  suitable  for  use  as  a  salad  oil,  cooking 
oil  or  for  such  other  purposes  as  cottonseed  oil,  or  similar  oils  have 
been  used,  the  product  being  superior  to  such  oils  in  keeping  qual- 
ities. 

A  further  advantage  of  the  new  product  lies  in  the  fact  that  the  dissolved 
stearin  therein  is  found  to  crystallize  most  readily,  which  quality  renders  the 
product  especially  suitable  for  winter  or  cold  pressing  for  salad  oil.  Accompany- 
ing cottonseed  oil  or  other  fatty  oils,  notably  seed  oils,  are  always  certain  im- 
purities. According  to  Lewkowitsch  (Technology  of  Oils  and  Fats)  "  these 
can  be  removed  for  the  most  part  by  steaming  or  washing  with  water,  followed 
by  bleaching  or  filtering,  but  even  after  this  purification  small  quantities  of 
non-glyceridic  substances  remain  dissolved.  Some  of  these  must  be  regarded 
as  entirely  foreign  substances,  e.g.,  traces  of  coloring  matter,  chromo  genetic 
substances  (producing  the  color  reactions  which  are  characteristic  of  some  oils 
and  fats)."  While  refined  choice  or  prime  yellow  cottonseed  oil  keeps  very 
well  in  dry  storage,  bleached  or  bleached  and  deodorized  cottonseed  oil  (pro- 
duced by  steaming)  does  not  keep  so  well  under  similar  storage  conditions  but 
tends  to  become  rancid  very  much  more  quickly  than  the  refined  undeodorized 
yellow  oil.  Cottonseed  oil  which  has  been  partially  hydrogenated,  does  not 
exhibit  this  tendency  toward  rancidity  even  though  bleached  oil  is  employed. 
Nor  does  the  hydrogenated  oil,  if  subsequently  deodorized,  develop  this  tendency. 
In  other  words,  hydrogenation  as  carried  out  in  the  manufacture  of  the  new 
product  appears  to  have  so  altered  or  destroyed  the  non-glyceridic  substances 
present  that  the  oil  has  been  markedly  improved  as  to  its  keeping  qualities. 
That  there  has  been  such  a  change  in  the  quantity  or  character  of  the  non- 

*J.  S.C.I.,  1918,  166  R. 

t  U.  S.  Patent  No.  1,187,999,  June  20,  1916. 


EDIBLE  HYDROGENATED  OILS  355 

glyceridic  substances  is  evidenced  by  the  fact  that  the  product  does  not  respond 
to  the  Halphen  test,  which  is  characteristic  of  cottonseed  oil. 

In  carrying  out  the  process  for  the  manufacture  of  the  product,  a  fatty  oil, 
for  instance  choice  or  prime  yellow  cottonseed  oil,  is  placed  in  ^a  closed  vessel 
and  caused  to  be  chemically  combined  with  hydrogen  in  the  presence  of  a  cata- 
lyzer. A  temperature  of  150°  to  200°  C.  has  been  satisfactorily  employed  and 
the  time  required  to  produce  the  desired  result  after  attaining  this  temperature 
is  from  five  to  thirty  minutes,  depending  upon  the  activity  and  proportion  of 
the  catalyzer  employed. 

Depending  upon  the  particular  cottonseed  oil  treated  by  the  process  the  iodine 
value  of  the  finished  product  varies  from  about  90  to  102.  Its  titre  (as  deter- 
mined by  the  Wolfbauer  method)  has  been  slightly  increased  during  the  process 
to  the  extent  of  from  about  -^  C.  to  -&0  C.  over  that  of  the  original  oil  treated. 
The  color  of  the  treated  product  is  usually  somewhat  lighter  than  the  original 
oil.  On  cooling  the  product  it  in  part  readily  crystallizes,  thereby  making  the 
separation  of  stearine  from  the  oil  much  easier  and  more  effective  for  "  winter 
pressing  "  for  salad  oil  than  is  the  case  with  ordinary  cottonseed  oil.  The  prod- 
uct responds  negatively  to  the  Milliau  test  for  cottonseed  oil. 

Brauer  *  notes  that  both  laboratory  experiments  and  those  made 
on  a  commercial  scale  indicate  that  hardened  fats  have  a  much 
greater  capacity  for  "  holding  "  water  than  untreated  fats,  and  that 
the  same  is  true  of  margarines  made  from  the  two  kinds  of  fats. 
Margarines  made  of  (a)  hardened  whale  oil  and  unhardened  linseed 
oil  (b)  hardened  linseed  oil  mixed  with  unhardened  oil,  and  (c)  tallow 
and  unhardened  linseed  oil,  contained  25.67  per  cent,  18.33  per  cent 
and  11.75  per  cent,  respectively,  of  moisture. 

The  fat-soluble  accessory  growth  substances  of  beef  fat  and  "  oleo- 
oil "  are  considered  important  food  elements  by  Halliburton  and 
Drummond.t  Margarines  containing  these  bodies  are  nutritively 
equivalent  to  butter.  On  the  other  hand  it  is  asserted  that  cocoa- 
nut  oil,  cottonseed  oil,  peanut  oil  and  hydrogenated  vegetable  oils 
contain  little  or  none  of  these  accessory  substances  and  that  mar- 
garines prepared  from  these  are  not  equal  to  butter  in  nutritive  value. 

The  introduction  of  hydrogenated  products  in  margarine  manu- 
facture according  to  Clayton  {  marks  a  great  technical  advance,  and 
one  which  is  likely  to  develop  very  rapidly  in  the  future.  He 
observes  that  an  objection  has  been  raised  by  Brauer  that  hardened 
oils  raise  the  moisture  content  of  a  margarine,  owing  to  their  prop- 
erty of  retaining  water,  much  in  excess  of  what  other  oils  do.  Brauer 
claims  to  have  proved  this  on  a  large  scale  on  many  occasions. 

*Z.  offent  Chem.,  22,  209;  Chem.  Zentr.,  1916,  II,  527;  Chem.  Abs.,  1917,  1699; 
Zeitsch.  angew.  Chem.,  1916,  29,  Ref  ,  492;  J.  S.  C.  I.,  1917,  98. 

t  Journal  of  Physiology,  1917,  51,  235-251.  J.  Chem.  Soc.,  1917, 112,  i,  673.  J.  S.  C.  I., 
1917,  1285. 

J  J.  S.  C.  I.,  1917,  1205. 


356  THE  HYDROGENATION  OF  OILS 

Clayton  notes  that  as  far  as  he  is  aware  such  a  difficulty  has  not 
been  met  with  in  British  factories,  and  in  any  case  the  problem 
admits  of  very  easy  solution.  The  use  of  hardened  oils  really  hinges 
upon  their  edibility  or  otherwise,  and  on  this  point  much  con- 
troversy has  raged.  Little  doubt  exists  as  to  their  being  thoroughly 
suitable  for  human  consumption,  since  they  are  assimilated  during 
human  metabolism  just  the  same  as  any  other  fats,  but  whether 
the  traces  of  metal  catalyst  almost  invariably  present  affect  the 
health,  was,  for  a  long  time,  a  dubious  matter.  Another  objection 
that  has  been  raised  against  the  use  of  these  oils  in  margarine  man- 
ufacture, is  that  good  products  may  be  prepared  from  bad  raw  mate- 
rial. As  a  particular  instance,  whale  oil  can  be  hydrogenated  to 
yield  a  tasteless,  odorless,  and  germ-free  fat,  physiologically  harmless. 
Suspicion  was  aroused  that  margarine  manufacturers  might  use 
cheap  and  unwholesome  fish  or  other  oils,  hardened  to  form  good, 
clean  products.  Much  controversy  has  centered  round  this  point. 
So  long  as  the  raw  material  was  unsound,  the  public  would  not 
sanction  the  final  margarine.  Maybe,  Clayton  adds,  there  will  be  a 
legal  fixing  of  the  raw  material  in  the  future.  At  any  rate,  such  a 
course  has  been  frequently  advocated,  especially  in  the  United  States. 
The  utility  of  hydrogenated  oils  in  the  manufacture  of  oleomar- 
garine receives  further  confirmation  by  Pickard,*  who  states  that  for 
the  purpose  hydrogenated  or  hardened  oils  are  used  in  considerable 
quantities.  He  further  states  that  when  the  process  is  properly 
handled,  the  melting-point  of  the  resulting  material  can  be  regulated 
to  a  nicety  and  the  oils  contain  no  appreciable  amounts  of  deleterious 
substances,  so  that  they  are,  therefore,  perfectly  wholesome  and,  in 
consequence,  legitimate  constituents  of  edible  products. 

Keebler  states  that  the  principal  difficulty  experienced  with  some  manufacturers 
of  nut  margarine  is  that  of  keeping  the  melting-point  above  75°  F.,  while  butter 
melts  about  92°  F.  However,  it  is  claimed  by  one  manufacturer  that  his  nut 
margarine  has  a  melting-point  of  107°  F.  Keebler  observes  that  this  possibly 
can  be  accounted  for  by  the  use  of  hydrogenated  oils. 

In  the  manufacture  of  leavened  bread  it  is  the  practice  to  add 
various  milk  products  to  improve  the  flavor,  etc.  The  addition  of 
milk  tends  to  retard  fermentation  by  yeast  and  Kohman,  Godfrey 
and  Asche  J  have  found  that  by  peptonizing  the  milk  the  fermenta- 
tion is  accelerated  rather  than  retarded. 

*  American  Food  Journal,  1918,  16. 

f  Am.  Food  Jour.,  1918,  363. 

J  U.  S.  Patent  No.  1,222,304,  April  10,  1917. 


EDIBLE  HYDROGENATED  OILS  357 

In  addition  to  milk  they  find  that  various  forms  of  cheese  may  he  employed 
and  that  it  is  preferable  to  mix  the  cheese  with  a  hydrogenated  fat  such  as 
hydrogenated  cottonseed  oil  having  a  melting-point  of  about  35°  to  40°  C. 
A  creamy  mixture  is  obtained  by  incorporating  these  ingredients  and  such  mix- 
ture may  be  readily  introduced  into  the  dough  batch  during  the  usual  mixing 
operation.  The  addition  of  the  hardened  fat  to  the  cheese  is  desirable  for  the 
further  reason  that  the  fat  replaces  a  part  or  all  of  the  shortening  agents  that  are 
ordinarily  added  to  bread.  Ten  parts  of  cheese  to  4  or  5  parts  of  the  hard- 
ened fat  may  be  employed  and  1  to  1|  lb.  of  this  mixture  may  be  used  to  100 
Ib.  of  flour. 

A  product  called  Vegetole,  manufactured  by  Armour  &  Co., 
according  to  the  American  Food  Journal,  June,  1917,  page  330,  is  a 
hydrogenated  cottonseed  oil,  without  flavor  and  fully  sterilized.  It 
is  stated  that  Vegetole  differs  slightly  from  lard  and  also  mixtures 
of  cottonseed  oil  and  oleostearine  and  that  it  also  has  different 
properties  from  cottonseed  oil.  It  is  observed  that  the  hydrogenated 
oils  form  a  class  by  themselves  and  bid  fair  to  constitute  a  most 
important  part  of  what  are  known  as  cooking  fats.  Vegetole  is 
sweet,  wholesome  and  nutritious  and  easily  digested  and  can  be 
used  for  all  purposes  for  which  lard  is  used.  As  a  shortening  agent, 
whether  in  bread,  pie  crust,  or  biscuits,  or  when  used  as  a  medium 
for  frying,  the  results  obtained  are  stated  to  be  excellent. 

According  to  Bernegau,*  fresh  white  of  egg  is  treated  at  about 
40°  C.  with  freshly  expressed  pineapple  juice  (containing  yeast  cells), 
and  the  resulting  liquid  mixed  with  sugar,  emulsified  with  fresh  egg 
yolk,  and  sterilized  by  heating,  yielding  an  emulsion  suitable  for 
blending  with  hydrogenated  oils  to  produce  an  edible  fat. 

Poulenc  Freres  f  claim  that  the  hydrogen ation  of  lecithin  may  be 
accomplished  by  the  aid  of  common  metals  and  their  oxides,  and  at  a 
temperature  below  that  at  which  lecithin  and  hydrolecithin  are 
decomposed,  by  having  the  catalyst  in  its  most  active  condition, 
obtained  by  slow  reduction  in  the  case  of  the  metals  and  by  dehy- 
dration of  the  hydroxides  at  a  low  temperature  in  the  case  of  the 
oxides;  by  vigorous  stirring  of  the  lecithin  so  as  to  expose  contin- 
ually fresh  surface  to  the  action  of  the  hydrogen,  and  by  working 
under  increased  pressure. 

Daughters  t  hydrogenated  oil  from  the  seed  of  the  wild  cucumber 
(iodine  No.  117)  using  a  nickel  catalyzer  and  a  temperature  of  220° 
to  240°  C.  The  hydrogenated  product  melted  at  29°  to  36°  C.  and  had 
an  iodine  number  of  76.6.  Feeding  experiments  with  mice  showed 
that  the  original  oil  and  the  hydrogenated  fat  were  non-poisonous. 

*  German  Patent  No.  295,351,  March  24,  1914. 

t  French  Patent  No.  478,193,  July  22,  1914;  J.  S.  C.  I.,  1916,  1131. 

JJ.  Ind.  Eng.  Chem.,  1918,  126. 


CHAPTER   XV 

USES  OF  HYDROGENATED   OILS  AND  THEIR  UTILIZA- 
TION IN  SOAP  MAKING 

USES  OF  HYDROGENATED  OILS 

Liquid  fats  and  fatty  acids  are  essentially  cheaper  than  solid  fats 
and  fatty  acids,  and  the  ability  to  prepare  from  ordinary  liquid  fatty 
oils  a  fatty  body  of  almost  any  desired  degree  of  consistency  or  hard- 
ness renders  hydrogenation  especially  attractive  in  the  production 
of  edible  fats  and  soap-making  materials.  These  are,  undoubtedly, 
two  of  the  most  important  applications,  although  hydrogenated  oils 
are  likely  to  have  a  rather  wide  use  in  the  arts.  In  the  manufacture 
of  insulating  compositions  and  lubricants,  for  example,  the  hydro- 
genated fats  may  be  used  to  advantage.  In  the  tanning  industry 
the  stearin  produced  by  hydrogenation  is  being  used  as  a  substitute 
for  oleo-stearin. 

The  physical  and  chemical  properties  *  of  hardened  oils,  particularly 
the  hardened  fish  oils,  indicate  that  these  products  are  useful  in  the 
manufacture  of  lubricants  and  that  they  may  be  used  as  a  substitute 
for  tallow  in  the  preparation  of  various  lubricating  compounds,  f  In 
compounding  preparations  of  this  character,  the  requisite  amount  of 
hardened  oil  is  added  to  the  oil  base  employed,  the  mixture  being 
heated  to  secure  satisfactory  incorporation,  and  then  is  cooled,  when 
it  is  ready  for  use.  The  better  grades  of  hardened  fish  oil  also  can 
be  used  alone  as  a  substitute  for  acid-free  machine  tallow. 

A  review  of  the  soap  trade  of  the  United  Kingdom  for  1913  is  significant  in 
indicating  decreased  requirements  of  several  of  the  staple  raw  materials,  which  con- 
dition, rather  than  suggestive  of  any  decline  in  the  production  of  soap,  marks  a 
greater  dependence  upon  supplies  which  have  been  brought  within  practical  oper- 
ation largely  through  the  hydrogenating  process  for  hardening  oils.  To  quote 
from  the  report  on  this  subject: 

"It  is  of  the  greatest  moment  that  the  European  soap  maker  has  found  in  the 
hardened  oils  produced  by  the  hydrogen  process  very  considerable  relief  from  factors 
that  must  have  driven  values  very  much  higher,  had  not  this  new  source  of  supply 
come  into  actual  operation." 

*  Seifen.  Ztg.  (1912),  1092. 

f  Hydrogenated  fats,  Leimdorfer  states  (Seifen.  Ztg.  (1913),  1317),  can  be  used 
in  the  preparation  of  lubricants  and  in  tanning  operations. 

358 


USES  OF  HYDROGENATED  OILS  359 

"  English  manufacturers  as  a  rule  are  quick  to  turn  to  advantage  any  opportunity 
to  exploit  new  methods  and  processes  in  their  industries,  and  the  recognition  of  the 
practical  application  of  hydrogenated  oils  in  such  an  important  field  as  soap  making 
is  a  development  of  much  interest  to  the  affected  trades  in  this  country,  where  the 
process  in  its  general  relationship  to  the  soap  and  lard  compound  industries  is  in  a 
more  or  less  experimental  stage.  According  to  the  English  soap  trade  report  the 
losses  in  three  of  the  leading  materials  available  for  home  consumption,  as  measured 
by  the  excess  of  imports  over  exports  in  1913,  were  3532  tons  of  tallow,  1656  tons  of 
palm  oil  and  2240  tons  of  cocoanut  oil.  Exports  of  soap  from  the  United  Kingdom 
last  year  were  heavier  (1732  tons),  while  imports  from  foreign  countries  were  lighter 
by  2194  tons.  As  a  result  of  the  strides  in  the  hardening  of  materials  for  soap  pro- 
duction by  hydrogenation,  whale  and  linseed  oils  are  now  accorded  an  established 
place  in  the  Kingdom's  soap  industry.  The  total  capacity  of  the  hardening  plants 
in  Europe,  including  the  United  Kingdom,  is  given  as  220,000  tons  of  oil,  although 
some  of  the  views  expressed  in  the  local  trade  place  it  to  300,000  tons.  A  good  part 
of  the  American  linseed  oil  export  trade  last  year  has  been  attributed  to  the  heavier 
requirements  for  the  soap  kettle  through  the  hydrogenation  process,  and  crushers 
and  dealers  have  been  buoyed  to  keener  expectations  for  this  year's  foreign  business. 
Conditions  in  other  fields  in  which  linseed  oil  enters  must,  however,  be  reckoned 
upon  as  contributing  factors.  Persistent  attempts  have  been  made  to  induce  our 
soap  makers  to  adapt  hardened  linseed  oil  to  their  service,  and  while  sales  of  round 
parcels  have  been  made  for  this  account,  so  far  as  is  known  none  of  the  purchasers 
has  been  encouraged  to  put  the  oil  into  actual  test.  The  favorable  market  condi- 
tions for  competing  fats  in  the  soap  field  may  have  accounted  for  the  attitude  of 
makers  toward  linseed  oil  for  this  particular  purpose." 

"Probably  the  greatest  headway  in  the  application  of  the  hydrogenating  hardening 
process  in  this  country  has  been  in  the  field  of  edible  products  in  which  cottonseed 
oil  has  entered  on  the  most  liberal  scale.  It  was  through  this  means  that  the  domes- 
tic consumption  of  refined  oil  during  the  last  crop  year  so  surpassed  the  general 
expectations  of  the  trade  that  the  principal  markets  abroad  were  scoured  last  sum- 
mer to  reclaim  any  supplies  of  our  oil  that  might  be  available,  and  foreign  producing 
sources  were  also  called  upon  to  help  relieve  the  stringency  here."  * 

Auerbachf  considers  the  hydrogenation  process  responsible  for  an  advance  in  the 
price  of  fish  oils  so  that  they  will  be  of  doubtful  benefit  to  the  soap  industry.  Also 
he  states  that  the  so-called  burned  odor  which  was  noticeable  in  soap  made  from- 
hardened  fats  is  said  to  have  been  overcome.  Besides  fish  and  whale  oil,  he  notes 
that  castor  oil  is  treated  to  some  extent.  The  hardened  castor  oil  is  used  for  insula- 
tion purposes  in  the  electrical  field. 


HYDROGENATED  OILS  IN  THE  SOAP  INDUSTRY 

The  developments  in  oil  hydrogenation  have  brought  to  the  soap 
industry  an  innovation  of  fundamental  importance  in  the  domain  of 
raw  materials.  The  soap  manufacturer,  no  longer  well  able  to  pur- 
chase the  best  grade  of  fats  in  face  of  the  high  prices  paid  by  the 
margarine  and  other  edible  fat  industries,  has  now  at  his  disposal  the 

*  Oil,  Paint  and  Drug  Rep.,  Feb.  2,  1914. 
t  Chem.  Ztg.,  37,  297. 


360  THE  HYDROGENATION  OF  OILS 

means  for  utilizing  lower  grade  materials  in  substitution  for  more 
costly  stock. 

By  hydrogenation,  oils  which  formerly  made  soaps  only  of  soft  con- 
sistency, now  yield  the  more  valuable  hard  soaps.  This  has  led  to  a 
very  rapid  development  of  the  art  with  respect  to  the  production  of 
soap-making  fats.  In  particular,  fish  and  whale  oils  have  been  made 
use  of,  because  these  oils  may 'be  completely  deodorized  by  the  addi- 
tion of  hydrogen. 

According  to  a  Japanese  chemist,  Tsujimoto,  the  odor  of  fish  oil  is 
due  almost  entirely  to  a  fatty  constituent  and  not  to  so-called  impuri- 
ties. This  fatty  constituent  is  clupanodonic  acid  having  the  formula 
Ci8H28O2,  which,  therefore,  by  the  addition  of  8  hydrogen  atoms, 
becomes  stearic  acid.  When  hydrogenated  down  to  an  iodine  num- 
ber of  about  50,  fish  oil  has  the  consistency  of  hard  tallow  and  the 
odor  of  fish  oil  is  wholly  absent.  Even  the  fishy  taste  is  scarcely  in 
evidence. 

For  soap  making  this  product  is  satisfactory  as  it  complies  with 
the  test  for  a  deodorized  fish  oil  suitable  for  soap  making  in  that  the 
odor  of  the  original  oil  is  not  apparent  when  ironing  laundered  goods 
on  which  such  soaps  are  used.  If,  however,  at  least  with  the  poorer 
grades  of  oil,  the  hydrogenation  is  not  carried  on  to  a  point  where 
the  iodine  number  is  approximately  50  or  less,  there  is  some  danger 
that  the  fishy  odor  will  become  apparent  during  the  ironing  operation. 

It  appears  not  improbable  that  unstable  odor-forming  nitrogenous 
impurities  in  fish  oil  add  hydrogen  during  the  hardening  process  and 
are  transformed  into  bodies  of  a  stable  character. 

Data  on  a  hydrogenating  plant  in  Norway  is  furnished  by  Commercial  Agent 
E.  W.  Thompson  of  the  Department  of  Commerce  (Consular  &  Trade  Reports, 
.Jan.  14,  1914,  171)  who  reports  that  during  the  summer  of  1913  an  oil-hardening 
plant  was  opened  at  Fredrikstad  by  De  Nordiske  Fabriker,  with  head  office  at 
Christiania.*  The  original  object  was  to  harden  whale  oil  for  the  soap  industry, 
but  as  the  result  of  experiments  with  edible  oils  the  plant  is  being  enlarged  to  a 
capacity  of  1000  barrels  a  day  with  the  expectation  of  hardening  cottonseed  and 
peanut  oils  for  the  margarine  makers.  If  this  plan  is  successful  it  may  double  the 

*  This  concern  is  said  to  be  a  German-Norwegian  company,  capitalized  at  about 
$833,500,  organized  to  work  a  new  German  method  of  hydrogenation.  The  Hafslund 
Falls  are  being  utilized  to  generate  the  electric  power  required  by  the  work  and  also 
to  manufacture  by  electrolysis  the  hydrogen  required  for  the  hardening  process  to 
which  the  purified  whale  oil  is  submitted  and  converted  into  a  solid  neutral  fat. 
The  daily  consumption  of  oil  is  about  300  barrels.  (Jour.  Ind.  and  Eng.  Chem. 
(1913),  608.)  .The  hardened  fat  has  a  melting  point  between  40°  to  50°  C.  and 
is  stated  to  be  odorless  and  tasteless.  Although  at  the  present  time  principally 
used  for  soap  making,  in  all  probability  in  due  course  the  material  will  be  employed 
in  the  manufacture  of  edible  fats.  (Scifen.  Ztg.  (1913),  1413.) 


USES  OF  HYDROGENATED  OILS  361 

consumption  of  cottonseed  oil  in  the  margarine  industry.  The  Norwegian  firm 
will  purchase  the  best  grades  of  cottonseed  and  peanut  oils,  and  will  also  harden  on 
toll.  Many  European  margarine  factories  are  experimenting  on  hardened  cotton 
and  peanut  oils  to  replace  copra  oil,  which  is  high  in  price.* 

Some  criticism  has  been  directed  at  the  use  of  hardened  oils  at  least  for  edible 
purposes  on  the  ground  that  nickel  is  used  in  the  process,  but  the  manufacturers 
say  that  although  nickel  is  generally  used  none  of  it  is  left  in  the. oil,  and  that  even 
if  it  were  it  is  harmless,  as  shown  by  many  tests  with  animals  and  with  human 
"poison  squads." 

Samples  of  Norwegian  hydrogenated  whale  oil  which  have  come  to 
the  author's  attention  are  of  exceptionally  high  quality. 

Whale  oil  of  the  grades  known  as  0  and  1  hydrogenate  readily  with 
nickel  as  a  catalyzer.  No.  2  is  somewhat  more  difficult  and  No.  3 
is  decidedly  troublesome  to  treat  without  special  refining. 

Chinese  wood  or  tung  oil  may  be  rendered  very  hard  by  thorough  hydrogena- 
tion  and  the  product  often  shows  the  property  of  expanding  on  solidifying  from  a 
melted  state,  forming  a  friable  mass  instead  of  a  firm  block.  Hardened  linseed  oil 
sometimes  exhibits  a  like  behavior. 

Hardened  chrysalis  oil  is  described  by  Tsujimoto  (Jour.  Chem.  Ind.  Tokio,  1914, 
No.  191  and  Chem.  Ztg.  Rep.  1914,  110).  Hydrogenation  was  carried  out  with  a 
nickel  catalyzer  and  traces  of  nickel  were  found  in  the  ash  of  the  hardened  product. 

Soya  bean  oil  has  become  an  important  raw  material  for  hydrogenation  purposes. 
(Seifen.  Ztg.,  1914,  348.) 

The  commercial  side  of  fat  hardening  is  discussed  to  some  extent 
by  Schicht  t  and  the  value  of  fish  and  whale  oils  in  this  field  is  con- 
sidered. The  probable  place  hardened  fats  will  assume  in  the  soap 
and  edible  fat  industry  is  discussed  in  Seifensieder  Zeitung  (1913, 
768). 

In  this  country  very  little  has  as  yet  appeared  in  the  literature 
regarding  the  application  of  hydrogenated  oils  in  soap  making,  but 
in  Germany  considerable  space  has  been  given  by  the  trade  journals 
to  discussions  of  the  subject.  Some  of  the  statements  are  of  a  very 
contradictory  character  as  is,  of  course,  to  be  expected  in  the  early 
stages  of  development  of  this  important  subject,  especially  in  view 
of  the  very  considerable  degree  of  empiricism  which  prevails  in  some 
branches  of  the  soap-making  industry. 

It  is  to  be  regretted  that  so  much  of  the  published  matter  relates 
to  products  offered  under  trade  names  such  as  Talgol,  Candelite  and 

*  Hardened  sunflower  oil  is  mentioned  in  Seifensieder  Zeitung  (1913),  611.  The 
Knowles  Oxygen  Company,  of  Wolverhampton,  England,  has  contracted  with  the 
Sunlight  Soap  Factory,  in  Port  Arthur,  to  erect  an  annex  to  the  plant  for  the  pro- 
duction of  the  hydrogen  necessary  for  hardening  palm  oil;  the  oxygen  is  to  be  col- 
lected and  sold. 

t  Seifen.  Ztg.  (1913),  287. 


362 


THE  HYDROGENATION  OF  OILS 


similar  hydrogenated  fish  and  whale  oils,  etc.,  of  the  Germania  Oel- 
werke  at  Emmerich,  but  while  soap  making  as  practiced  in  Germany 
differs  in  several  respects  from  the  practice  in  this  country,  it  is  be- 
lieved the  work  abroad  will  prove  at  least  suggestive  if  not  instruc- 
tive.* 

In  the  following  an  attempt  has  been  made  to  briefly  review  the 
more  important  contributions  in  this  connection. 

Garth  f  states  that  fish  and  whale  oils  are  the  raw  materials  for  a 
considerable  proportion  of  the  hydrogenated  products  which,  up  to 
the  present  time,  have  found  application  in  soap  making.  Being 
relatively  low-priced  raw  material  many  attempts  have  been  made  to 
make  cheap  soaps  from  fish  oil.  These  attempts  in  the  past  have 
been  unproductive  because  the  objectionable  odor  reappears  after 
goods  are  laundered.  Hence  there  are  many  proposals  directed 
toward  the  production  of  odorless  fish  oil.  As  is  known  fish  oil  con- 
tains nitrogenous  compounds  and  certain  of  the  lower  fatty  acids 
arising  from  decomposition  of  the  fish  before  the  oil  is  expressed. 
Most  of  the  proposals  are  based  upon  the  assumption  that  these  sources 
of  the  evil  odor  can  be  removed  by  the  action  of  energetically-reacting 
bodies  such  as  sulfuric  acid  and  the  like.  However,  neither  treat- 
ment with  strong  acids  nor  distillation  with  superheated  steam  pro- 
duce unobjectionable  products.  By  hydrogenation  the  disagreeable 
odor  disappears;  nevertheless,  there  always  remains  an  odor  similar 
to  that  of  distilled  olein  which,  however,  is  completely  concealed  if 
the  product  is  worked  up  with  a  goodly  proportion  of  other  fats. 

GarthJ  observes  that  the  hydrogenated  fats  which  have  been 
used  in  the  soap  manufacture  appear  in  the  trade  as  Talgol,  Talgol 
extra,  Candelite,  Candelite  extra,  Crutolein,  Talgin,  etc.  Talgol 
has  a  melting  point  of  35°  to  37°  C.,  and  an  iodine  number  of  65  to 
70.  Talgol  extra  melts  at  42°  to  44°  C.  and  the  iodine  number  is 
45  to  55.  The  Candelite  products  are  harder,  Candelite  melting  at 

*  In  England  one  large  concern  is  offering  several  grades  of  hardened  fat  ranging 
as  follows: 


Iodine  No. 

M.P. 

Titer 

Al 

50 

40-42 

36 

A2 

85 

28-30 

32 

Cl 

60 

44-46 

45 

C2  .                         

75 

35-37 

36 

t  Seifen.  Ztg.  (1912),  1278. 
t  Seifen.  Ztg.  (1912),  1279. 


USES  OF  HYDROGENATED  OILS 


363 


48°  to  50°  C.,  and  having  an  iodine  number  of  15  to  20,  while  Candelite 
extra  melts  at  50°  to  52°  C.  and  exhibits  an  iodine  number  of  5  to  10.* 
Heller  f  furnishes  the  following  data  on  these  products: 


Acid  No. 

Saponification 
No. 

Unsaponi- 
fiable 

Iodine 
No. 

Talgol        

3  5 

190  7 

0  33 

63  9 

Talgol  extra  

3.8 

190  5 

0.31 

36   1 

Candelite  

3.8 

190.4 

0.41 

18  4 

Candelite  extra  

4.4 

188.4 

0.52 

10.4 

FATTY  ACIDS 


Melting  point 

Titer 

Acid  No. 

Talgol 

38  5 

34  6 

199  7 

Talgol  extra  

45  5 

43  5 

199  9 

Candelite  

48  5 

47  4 

198  9 

Candelite  extra  

51.8 

50.5 

199.9 

Schaal  has  reported  t  the  results  of  his  observations  on  the  two 
products  Talgol  and  Candelite  derived  by  hydrogenation  of  fish  oil, 
etc.,  and  has  called  attention  to  the  adaptability  of  these  hardened 
fats  in  the  production  of  soap  base  or  milled  soap.  Both  Talgol  and 
Candelite  have  a  tallowy  appearance  with  this  difference,  that  one  is 
softer  and  one  is  harder  than  tallow.  At  first  glance  one  is  likely  to 
regard  these  fats  as  similar  to  high-grade  soap  tallow,  but  the  odor  of 
the  product  immediately  shows  this  is  not  the  case.  The  odor  is  not 
disagreeable  and  in  fact  resembles  some  grades  of  tallow.  It  is  sug- 
gestive of  the  cheesy  odor  given  off  by  tallow  which  has  been  stored 
for  a  considerable  time  in  warm  weather.  Of  the  two  products  Talgol 
and  Candelite,  the  odor  in  the  latter  is  less  noticeable. 

In  his  first  investigations  Schaal  simply  replaced  a  part  of  the  softer 
fats,  as  he  thought  Talgol  would  lose  its  firm  consistency  during  the 

*  The  Olwerke  Germania  has  trademarked  in  the  German  Patent  Office  the  words 
Andelite,  Candolit,  Cancellit,  Coryphol,  Doratol,  Dural,  Durettol,  Durolit,  Durotin, 
Durotal,  Duru,  Durutol,  Jutol,  Jutolin,  Kandel,  Kandelin,  Kandetil,  Kandorit, 
Kerzenit,  Kritolit,  Krunotin,  Krutello,  Krutol,  Krutolin,  Talgela,  Talgelin,  Talgol 
and  Urutol.  (Taschenkalender  f.  d.  Oel  und  Fett  Industrie,  1914.) 

t  Seifenfabrikant  (1912),  No.  31. 

t  The  results  of  investigations  by  Schaal  on  the  utilization  of  hardened  oils  in 
soap  manufacture  are  published  in  the  Seifensieder  Zeitung  (1912),  821,  846,  954 
and  979;  (1913),  173,  and  in  a  book  entitled  Die  Moderne  Toiletteseifen-Fabrikation, 
Augsburg,  1913,  to  which  reference  should  be  had  for  detailed  description. 


364  THE  HYDROGENATION  OF  OILS 

boiling  operation  and  would  return  to  a  consistency  approaching  that 
of  the  original  oil.  This  assumption  proved  to  be  unwarranted  as 
tests  with  small  samples  showed  that  the  Talgol  fatty  acids  were  as 
hard  as  the  Talgol  itself.  The  first  fat  mixture  used  for  preparing  a 
soap  consisted  of  the  following : 

40  parts  tallow. 
15  parts  Talgol. 
30  parts  bone  fat. 
15  parts  cocoanut  oil. 

No  rosin  was  used  as  it  was  desired  to  determine  the  influence  of 
the  Talgol  odor.  During  the  boiling  the  odor  of  Talgol  was  plainly 
in  evidence,  much  more  noticeable  in  fact  than  could  be  observed 
afterwards  in  the  finished  soap.  The  dried  curd  exhibited  a  wholly 
agreeable  odor  in  which  the  characteristic  odor  of  Talgol  could  not  be 
detected,  and  no  odor  was  in  evidence  of  a  nature  calculated  to  affect 
the  perfume.  The  soap  was  not  perfumed,  but  was  wrapped  in  paper 
and  laid  aside  a  few  weeks  for  further  observation.  In  another  trial 
the  tallow  was  reduced  and  the  Talgol  increased  in  amount,  the 
formula  being: 

25  parts  tallow. 

35  parts  Talgol. 

30  parts  bone  fat. 

10  parts  cocoanut  oil. 

The  saponification  progressed  satisfactorily,  indicating  that  Talgol 
readily  united  with  alkali.  As  the  bone  fat  employed  was  of  exception- 
ally dark  color,  the  soap  was  bleached  in  the  kettle  with  0.2  per  cent 
Blankit.  The  dried  product  had  a  fine  ivory  white  appearance,  but 
the  odor  of  Talgol  was  apparent  although  not  so  pronounced  as  to 
render  the  soap  unusable.  This  soap  base  milled  very  smoothly  and 
easily,  giving  an  excellent  finish.  In  another  trial  5  per  cent  of  rosin 
was  introduced  with  improvement  in  the  odor  of  the  soap  base. 

The  milled  and  perfumed  soap  was  kept  under  observation  and  it 
was  noted  that  some  perfumes  were  affected  by  the  Talgol  odor.  A 
person  with  a  keen  sense  of  smell  would  immediately  detect  the 
presence  of  Talgol.  Tests  were  conducted  with  a  number  of  perfumes* 
including  hyacinth,  lilac,  rose,  pathouly  and  violet,  each  cake  being 
separately  wrapped  in  parchment  paper.  It  was  found  that  the  two 
first-mentioned  perfumes  were  more  sensitive  to  the  presence  of  Tal- 
gol smell  and  gave  a  momentary  impression  that  the  soap  had  become 

*  Schaal  gives  a  number  of  perfume  formulae  for  hydrogenated  oil  soaps  in 
Seifen.  Ztg.  (1912),  979. 


USES  OF  HYDROGENATED  OILS  365 

rancid;  the  rose  was  slightly  affected  while  the  other  samples  were 
not  noticeably  changed.  Schaal  reaches  the  conclusion  that  the 
highest  grade  of  toilet  soap  perfumed  with  delicate  essential  oils  is 
affected  by  the  use  of  Talgol  or  Candelite  and  that  these  hardened 
oils  will  not  find  an  application  here.  Such  soaps  are,  however,  sold 
only  to  very  fastidious  trade  and  require  in  any  case  perfumes  of  the 
very  highest  grade.  On  the  other  hand,  in  manufacturing  ordinary 
grades  of  toilet  soap  which  are,  of  course,  made  in  enormous  quan- 
tities, up  to  about  35  per  cent  of  Talgol  or  Candelite  may  be  employed 
advantageously  in  the  fat  stock.  As  regards  solubility  in  water  and 
free  lathering  properties,  Schaal  found  Talgol  or  Candelite  to  afford 
satisfactory  results,  the  soaps  which  he  prepared  forming  a  lather 
immediately  which  was  thick  and  voluminous,  acting  in  fact  like  any 
standard  soap.  It  is  reported  that  the  Olwerke  Germania  has  been 
successful  in  producing  a  completely  odorless  product  at  a  somewhat 
higher  cost.  If  such  a  deodorized  product  can  be  put  out  at  reason- 
able price,  it  will  be  possible  to  make  toilet  soaps  of  the  highest  grade 
with  hardened  fats  derived  from  relatively  cheap  oils. 

Of  Talgol,  Schaal  notes  that  the  fat  is  readily  deprived  of  its  glycer- 
ine and  especially  well  by  the  Krebitz  process,*  and  soaps  made  from 
this  stock  are  prime  products. 

Schaal  states  that  so  long  as  these  hardened  fats  are  not  entirely 
odorless,  as  indicated  they  cannot  be  advanced  for  the  manufacture 
of  soap  stock  of  the  first  class.  For  these,  the  best  beef  tallow,  etc., 
must  remain  the  raw  material,  for  this  class  demands  the  best  that  the 
soap  industry  can  produce.  Talgol  is  therefore  considered  suitable 
only  for  working  up  into  soap  stock  of  second  and  third  grade.  In 
these  soaps  the  price  of  raw  material  plays  a  considerable  role,  and 
thus  Talgol  proves  an  advantageous  substitute  for  tallow.  Pure  Tal- 
gol soap  has  too  little  lathering  power  and  as  its  odor  is  also  objection- 
able it  is  not  advisable  to  allow  the  addition  of  Talgol  to  rise  above 
40  per  cent.  The  lathering  power  will  be  considerably  better  if  10  per 
cent  of  palm  kernel  or  cocoanut  oil  is  worked  in  and  the  solubility  of 
the  soap  is  also  much  increased.  If,  however,  60  per  cent  of  other  fats 
are  present,  bad  lathering  is  prevented,  and  the  product  meets  the  re- 
quirements of  the  trade.  The  yield  of  pure  salted  soap  on  the  average 
is  165  per  cent. 

The  following  are  some  recipes  given  by  Schaal  for  soap  stock  of  two 
grades. 

*  The  Krebitz  process  is  recommended  for  the  treatment  of  hardened  fats  in  the 
manufacture  of  toilet  soaps.  (Seifen.  Ztg.,  1914,  391.) 


366  THE  HYDROGENATJON  OF  OILS 

Soap  Stock,  Second  Grade 

(1)  30  parts  Talgol  extra;  (2)   40  parts  Talgol  extra; 

40  parts  beef  tallow;  25  parts  beef  tallow; 

15  parts  peanut  or  corn  oil;  20  parts  peanut  or  corn  oil; 

15  parts  cocoanut  oil.  15  parts  cocoanut  oil. 

Soap  Stock,  Third  Grade 

(1)   40  parts  Talgol  extra;  (2)   40  parts  Talgol  extra ; 

15  parts  beef  tallow;  30  parts  oleomargarine  waste, 

30  parts  oleomargarine  waste,  bone  fat,  hide  fat,  etc. ; 

bone  fat,  hide  fat,  etc.;  20  parts  bleached  palm  oil; 

10  parts  palm  kernel  oil  or  6  parts  cocoanut  oil; 

cocoanut  oil;  4  parts  rosin. 
5  parts  rosin. 

It  may  be  noted  that  with  each  increase  in  the  amount  of  Talgol, 
a  similar  increase  in  the  amount  of  softer  fats  is  demanded.  Talgol 
extra  is  a  rather  hard  fat  and  easily  permits  a  considerable  addition 
of  fluid  fats,  producing  a  pliable  plastic  soap  base  which  can  be  easily 
milled.  Talgol  like  tallow  is  saponifiable  with  some  difficulty  and 
for  the  complete  combination  of  it  with  alkali,  boiling  for  a  number  of 
hours  is  required.  The  boil  must  be  conducted  with  weak  lyes  of 
15  to  20  degrees  in  order  to  get  a  good  combination  of  fat  and  lye. 
With  respect  to  the  odor  of  the  soap  it  is  an  advantage  if  the  reaction 
between  the  fat  and  lye  is  extended  over  as  long  a  period  as  possible, 
since  the  odor  of  Talgol  thus  almost  completely  disappears.  When 
possible  the  Talgol  material  should  be  well  blown  with  steam  in  the 
kettles,  as  by  this  treatment  the  odor  is  almost  completely  removed. 

The  resulting  soap  base  displays  absolutely  no  difference  from  that 
of  a  straight  tallow  stock,  and  works  up  on  the  machines  exactly  as 
a  soap  from  beef  tallow;  indeed  it  may  be  said  that  milled  soap  from 
Talgol  has  a  finer,  cleaner  and  whiter  look  than  that  made  without 
it.  The  odor  may  be  permanently  concealed  in  finishing  the  soap 
by  means  of  appropriate  perfumes. 

The  tests  made  by  Schaal  of  Talgol  as  a  constituent  of  cold  process 
soaps  led  to  the  conclusion  that  it  only  has  value  in  combination  with 
cocoanut  oil.  The  saponification  of  Talgol  may  be  accomplished 
with  strong  tepid  lyes  if  the  following  conditions  are  observed.  First 
the  temperature  of  the  fat  at  the  moment  of  contact  with  the  lye 
must  be  at  least  50°  C.  and  on  cold  days  about  55°  C.  It  is  desirable 
to  warm  the  lye  to  25°  to  30°  C.  before  incorporating.  It  often 
happens  on  mixing  that  the  whole  mass  suddenly  solidifies  so  that  the 
mixture  must  be  warmed  to  liquefy.  Even  when  the  temperature 
of  the  bath  is  higher  than  the  figures  given,  solidification  takes  place 


USES  OF  HYDROGENATED  OILS  367 

on  running  in  the  cold  lye,  or  at  least  small  lumps  are  formed.  The 
union  of  the  fat  and  lye  takes  place  very  quickly;  the  mass  becomes 
solid  in  a  short  time  and  can  be  framed.  On  this  account  the  frames 
must  be  ready  at  hand.  In  the  frames  a  rather  strong  reaction  sets 
in,  and  heat  is  generated.  The  frames  should  be  well  covered  to 
take  advantage  of  this  rise  in  temperature.  The  finished  soap  is  very 
hard  and  almost  brittle  in  character  and  on  this  account  must  be  cut 
while  fresh.  It  has  a  fine  white  color,  but  is  not  transparent.  The 
odor  is  not  unpleasant,  and  varies  with  the  fat  used;  it  can  be  com- 
pletely covered  by  oil  of  citronella  or  lavender.  Artificial  oil  of  bitter 
almonds  is  less  adapted  to  permanently  cover  the  Talgol  odor. 
The  following  is  a  useful  formula: 

25  parts  Talgol, 

25  parts  Ceylon  cocoanut  oil, 

5  parts  castor  oil, 
28  parts  caustic  soda  lye,  37°  Be. 

The  mixture  of  fats  at  a  temperature  of  45°  to  50°  C.  is  stirred  well 
with  the  lye,  which  need  not  be  warmed.  In  about  one-half  hour 
reaction  is  under  way  and  the  product  should  at  once  be  framed.  If 
delayed  longer,  the  mass  becomes  almost  in  a  moment  solid  and  must 
be  warmed  to  soften.  This  is  unnecessary  if  the  frames  are  ready  at 
hand  as  above  cautioned.  This  soap  heats  up  strongly  in  the  frames 
and  on  cooling  is  plastic  with  a  somewhat  transparent  look.  It 
lathers  freely  like  a  shaving  soap  and  when  properly  perfumed  is  an 
excellent  product.  Such  a  soap  is  well  adapted  for  pressing,  which 
gives  it  a  fine  solid  appearance. 

For  cocoanut  oil  soaps  which  are  to  be  filled,  25  per  cent  of  Talgol 
is  recommended.  Such  soaps  cut  and  press  well  and  have  a  good 
solid  feel.  The  batch  should  be  maintained  at  a  temperature  of 
40°  C.  when  stirring,  lest  the  soap  get  too  solid  before  the  filling  is 
worked  in.  If  this  temperature  is  maintained  no  trouble  need  be 
feared  with  the  lye  or  the  filling.  In  weighing  off  the  oil  it  is  to  be 
noted  that  the  cocoanut  oil  should  be  first  introduced  and  then  the 
Talgol.  Otherwise  the  latter  sticks  to  the  side  of  the  kettle  and  the 
entire  mixture  then  has  to  be  made  hotter  than  is  necessary.  75  per 
cent  of  filling  can  be  incorporated  with  25  per  cent  of  Talgol,  giving 
a  yield  of  225  per  cent  without  danger  that  the  filling  will  settle  out 
or  fail  to  be  held  up.  The  soap  is  moulded  as  soon  as  thick  and  the 
moulds  left  covered  for  two  hours.  The  cooled  soap  is  hard  and 
tenacious  but  still  may  be  readily  pressed.  For  filling,  any  desired 
solution  of  salt,  potash  and  sugar  in  water  may  be  employed. 


368  THE  HYDROGENATION  OF  OILS 

The  following  is  an  appropriate  recipe  for  a  soap  of  this  class: 

22  2  kilos  Ceylon  cocoanut  oil, 
1\  kilos  Talgol, 

16|  kilos  caustic  soda  lye,  37°  Be., 
22|  kilos  filling  solution, 

perfumed  with  200  grams  of  oil  of  citronella  or  200  grams  of  lavender 
or  100  grams  of  each  oil. 

For  soaps  with  more  than  75  per  cent  filling  and  yields  of  250  per 
cent  and  over  it  is  best  to  conduct  the  process  in  the  warm  way. 

A  cold  process  shaving  soap  made  from  80  per  cent  Talgol  extra 
and  20  per  cent  cocoanut  oil  exhibited  satisfactory  lathering  prop- 
erties, but  in  spite  of  strong  perfuming  the  Talgol  odor  eventually 
reappeared,  especially  at  the  surface  of  the  cakes.* 

In  a  discussion  of  available  substitutes  for  palm  kernel  oil  f  it  is 
stated  that  hardened  fish  or  whale  oil  such  as  Talgol  cannot  be  used 
as  a  substitute  for  palm  kernel  oil.  The  peculiar  musty  odor  of  Tal- 
gol, which  to  be  sure  no  longer  resembles  that  of  the  original  oil,  is, 
however,  decidedly  penetrating.  Several  grades  of  soap  made  with 
Talgol  and  Crutolein  yielded  a  soap  of  too  pronounced  an  odor  to  be 
marketable.  Soap  containing  these  hardened  products  was  made  into 
a  soap  powder  and  although  the  percentage  of  the  hardened  fat  in 
this  product  was  low,  its  presence  was  still  detectable  by  the  odor. 
It  is,  however,  stated  that  if  means  can  be  found  for  the  removal  of 
this  characteristic  odor,  the  situation  as  regards  the  general  utility  of 
these  hardened  fats  will  be  entirely  altered. { 

*  .Weber,  Seifen.  Ztg.  (1913),  421. 

t  Seifen.  Ztg.  (1913),  312. 

t  Neither  tallow,  palm  kernel  or  cocoanut  oil  can  be  completely  substituted  in 
soap  making  by  hardened  fish  or  whale  oil,  but  the  latter  may  be  used  to  advantage 
as  an  addition  fat  in  laundry  soaps.  (Seifenfabrikant  (1913),  30;  Zeitsch.  f.  ang. 
Chem.  (1913),  310.) 

Leimdorfer  (Seifen.  Ztg.  (1913),  284  and  310)  treats  of  hardened  fats  with  special 
reference  to  the  soap  industry. 

The  addition  of  hardened  oil  to  other  soap  stocks  is  advantageous  for  lowering 
costs  and  gives  a  satisfactory  product  when  not  used  to  excess.  When  caustic 
potash  is  used  for  saponifying  a  mixture  of  65  per  cent  cottonseed  oil  and  35  per  cent 
Candelite  the  soap  does  not  grain  but  remains  clear.  (Seifenfabr.,  33,  30.) 

Hardened  oils  have  faced  several  problems.  The  technician  at  first  looked  upon 
them  with  distrust.  The  peculiar  odor  of  these  fats  has  caused  considerable  criti- 
cism and  their  surprisingly  white  color  has  been  looked  upon  as  unnatural.  The  soap 
produced  with  this  stock  has  a  characteristic  structure  and  its  appearance  changes 
somewhat  in  storage.  The  distrust  evidenced  toward  hydrogenated  fat  is  shown, 
however,  to  be  unjustified. 


USES  OF  HYDROGENATED  OILS  369 

Hardened  oils  when  used  in  soaps  *  in  the  proportion  of  50  to  80  per 
cent  give  products  which  are  very  hard,  dissolve  with  difficulty  and 
do  not  lather  readily.  The  saponification  is  also  said  to  be  somewhat 
slower  than  with  ordinary  soap  fats.  When  about  30  per  cent  of 
hardened  oil  is  used  the  soap  is  satisfactory. 

Semi-boiled  soaps  were  made  as  follows: 

(1)  50  parts  each  of  cocoanut  oil  and  hardened  oil  were  saponified 
at  80°  C.  with  38  degree  caustic  soda  lye.     The  lye  was  stirred  into 
the  hot  oil  mixture  and  the  kettle  kept  covered  until  a  well  saponified 
product  was  obtained.     A  little  alkali  was  added  to  show  a  faint  excess 
alkali  by  phenol  phthalein.     After  short  standing  the  soap  was  framed 
and  cooled.     It  had  a  fine  white  color,  but  possessed  a  sharp  odor 
(which  however  can   be  diminished  or  removed  by  boiling).     The 
lathering  qualities  appeared  less  pronounced  than  was  the  case  with 
a  soap  made  from  \  tallow  and  \  cocoanut  oil.     The  hardened  oil 
soap  dissolved  more  slowly  in  water.f 

(2)  80  per  cent  hardened  oil  and  20  per  cent  cocoanut  oil  saponified 
in  the  same  way  was  very  hard  and  white  but  showed  no  lathering 
properties.     The  odor  was  slightly  rancid. 

(3)  30  per  cent  hardened  oil,  25  per  cent  peanut  oil,  30  per  cent 
cocoanut  oil  and  15  per  cent  rosin  showed  a  rate  of  saponification 
which  was  normal;  the  soap  was  yellowish,  the  odor  and  solubility 
satisfactory,  but  the  lathering  properties  were  not  quite  as  good  as 
normal  soap. 

The  conclusion  reached  with  the  hardened  oils  tested  was  that  very 
hard  soaps  could  be  produced  which  would  show  great  economy  in 
use,  that  they  gave  a  poorer  lather,  that  the»re  was  some  odor  over 
and  above  that  resulting  in  use  of  tallow,  and  that  the  saponification 
was  slightly  slower,  t  Hardened  oils  were  also  found  to  give  dark 

An  example  of  a  satisfactory  soap  base  for  toilet  soaps  is  given  in  the  following 

formula:  15  parts  cocoanut  oil, 

45  parts  tallow  oil, 
40  parts  Talgol, 

and  suggestions  are  made  for  the  manufacture  of  laundry  soaps,  white-grained 
soaps,  cold  process  soaps,  transparent  glycerine  soaps,  soap  powder,  etc.  The 
hardened  fat  is  not  suitable  for  the  production  of  transparent  soft  soaps  or  natural 
grain  soaps.  (Seifenfabrikant  (1912),  1229,  1257.) 

*  Seifen.  Ztg.  (1912),  660. 

t  Weber  (Seifen.  Ztg.  (1913),  421)  gives  a  somewhat  complicated  procedure  for 
making  soap  base  with  hardened  oils  of  the  Talgol  type. 

\  Leimdorfer  (J.  S.  C.  I.,  1914,  206)  states  that  the  speed  of  saponification  of 
hydrogenated  fats  is  greater  than  the  analogous  natural  fat  (tallow)  under  similar 
conditions. 


370  THE  HYDROGENATION  OF  OILS 

fatty  acids  by  the  Twitchcll  process  and  odor  of  the  fatty  acids  was 
not  regarded  as  entirely  satisfactory. 

A  procedure  for  making  milled  soap  base  from  hardened  oil  *  in- 
volves the  formula: 

1200  pounds  Talgol  extra, 
1200  pounds  beef  tallow, 
600  pounds  Ceylon  cocoanut  oil. 

The  tallow  first  was  placed  in  the  kettle  and  saponified  with  20 
degree  caustic  soda  lye  somewhat  diluted  with  water.  A  little  salt 
was  added  at  the  beginning  of  the  boiling  to  prevent  lumpiness.  The 
Talgol  extra  was  then  added  and  saponified.  This  addition  gave  the 
stock  a  different  odor  which,  however,  diminished  as  the  operation 
progressed  and  the  final  product  possessed  the  desired  odor  of  good 
neutral  soap.  After  slow  boiling  for  several  hours  the  stock  was 
allowed  to  stand  over  night  after  it  had  been  ascertained  that  a 
sufficient  excess  of  alkali  was  present.  Subsequently  the  soap  was 
salted  out  with  24  degree  brine,  and  after  settling  the  spent  lye  was 
replaced  with  8  degree  caustic  soda  lye.  Slow  boiling  was  continued 
for  several  hours  to  complete  the  saponification  and  improve  the  odor. 
After  settling  over  night  the  lye  was  removed  and  the  cocoanut  oil, 
with  the  required  amount  of  30  degree  caustic  soda  lye,  was  introduced. 
Less  caustic  soda  was  needed  than  the  calculated  amount  for  the  cocoa- 
nut  oil  employed  as  the  saponified  stock  contained  some  entrained 
lye.  A  small  quantity  of  weak  brine  was  added  and  boiling  continued 
for  several  hours.  Strong  brine  was  then  introduced  to  salt  out  the 
saponified  product.  After  standing  36  hours  the  stock  was  withdrawn, 
solidified  in  cooling  apparatus  and  subsequently  dried.  A  relatively 
low  temperature  was  used  in  drying  yet  no  difficulty  was  experienced 
in  securing  a  rapid  removal  of  the  moisture.  The  addition  of  hydro- 
genated  oil  to  soft  fats  prevents  adhesion  of  the  resulting  soap  in  the 
drying  apparatus. 

The  soap  base  machined  perfectly  and  yielded  a  first-class  finished 
product.  Samples  of  the  soap  were  stored  for  several  months  and 
then  given  to  unbiased  persons  for  criticism  without  informing  these 
judges  that  hydrogenated  oil  had  been  used  in  the  make-up  of  the 
soap.  All  united  in  declaring  the  product  an  excellent  one  and 
the  freshness  of  the  perfume  was  noted.  The  lather  exhibited  by  the 
milled  soap  was  of  a  good  stiff  consistency  and  quite  lasting,  resembling 
that  afforded  by  a  shaving  soap. 

On  examination,  the  glycerine-containing  lyes  derived  in  the  fore- 

*  Seifen.  Ztg.  (1913),  334  and  368. 


USES  OF  HYDROGENATED  OILS  371 

going  method  of  saponification  were  found  to  resemble  those  obtained 
when  beef  tallow  was  used  without  additions  of  the  hydrogenated 
fat. 

Garth  *  states  that  a  grained  soap  having  a  desirable  hard  feel  may 
be  obtained  by  the  use  of  Talgol,  as  has  been  proven  by  practical 
experience.  Also  a  larger  yield  is  obtained,  and  since  the  Talgol 
products  are  cheaper  than  tallow  itself,  a  double  advantage  is  secured. 
The  hydrogenated  fat  finds  application  not  only  in  textile  and  laundry 
soaps  but  also  in  soap  base  intended  for  toilet  soap  manufacture. 
By  itself  Talgol  is  seldom  used.  In  the  case  of  laundry  soap  25  to 
30  per  cent  of  rosin  should  be  employed.  As  to  shaving  and  trans- 
parent glycerine  soaps,  see  Seifen.  Ztg.  (1913),  954.  Too  large  an 
addition  of  the  Talgol  to  grained  soap  causes  the  framed  soap  to  check 
badly  on  standing. 

Bergo  f  criticizes  hardened  oil  from  the  point  of  view  of  soap  making, 
stating  that  only  a  very  moderate  percentage  of  the  hardened  oil  in 
conjunction  with  other  oils  and  fats  can  be  used,  otherwise  the  lather- 
ing quality  of  the  soap  is  seriously  influenced.  The  somewhat  musty 
odor  which  soaps  containing  30  per  cent  or  more  hardened  oil  show, 
may  be  diminished  or  eliminated  through  long  boiling,  or  by  repeated 
washing,  or  by  the  addition  of  a  suitable  perfuming  agent;  but  long 
boiling,  as  well  as  repeated  salting  out  or  covering  the  odor  with  per- 
fumes, is  costly.  Another  objection,  namely,  that  soaps  made  with 
additions  of  hardened  oil  lose  in  lathering  quality,  is  a  more  important 
consideration  than  the  odor.  The  consumer  looks  upon  good  solu- 
bility and  strong  lathering  properties  as  essential  in  soaps.  Bergo 
thinks  if  success  is  not  attained  in  removing  this  objectionable  feature, 
the  application  of  hydrogenated  oils  in  the  soap  industry  will  remain 
very  limited. 

A  further  obstacle  on  a  large  scale  is  the  color  of  the  product  ob- 
tained by  autoclave  saponification.  Hardened  oil,  which  as  a  neutral 
fat  shows  a  beautiful  white  color,  gives  fatty  acids  which  in  spite  of 
all  possible  precautions  in  the  autoclave  treatment  and  even  with  the 
use  of  bleaching  material,  such  as  decrolin  and  the  like,  appear  of  a 
yellow  color  and  in  consequence  are  not  suitable  for  white  soaps.  If, 
he  states,  we  do  not  saponify  these  oils  for  fatty  acids,  but  process 
them  as  neutral  fats  and  saponify  with  caustic  alkali,  then  the  differ- 
ence in  price  as  compared  with  other  available  fats  and  oils  is  so  far 
reduced  that  it  is  a  question  whether  the  soap  manufacturer  will  use 
such  artificially  hardened  oils  and  thereby  reduce  the  quality  of  the 

*  Seifen.  Ztg.  (1912),  1279. 
t  Seifen.  Ztg.  (1912),  1333. 


372  THE  HYDROGENATION  OF  OILS 

soap.  The  hopes  of  the  soap  maker  have  been  based  on  the  supposition 
that  a  fat  which  would  be  a  substitute  in  the  manufacture  of  white 
grain  soaps  would  be  found,  because  the  fats  and  oils  now  available 
for  making  white  soaps  are  very  few;  while  for  yellow  soaps  a  whole 
series  of  fats  are  obtainable  and  these  Bergo  regards  as  practically 
no  more  costly  than  hardened  oil  costs  to-day.  Hence  he  thinks  these 
new  raw  materials  offer  no  advantage  for  the  soap  industry  in  Ger- 
many on  account  of  their  price  and  defects  mentioned.* 

In  contrast  to  the  views  of  Bergo,  a  writer  in  Seifen.  Ztg.  (1912),  101, 
refers  to  the  comment  that  hydrogenated  fish  oil  gives  dark  unsightly 
soaps  which  do  not  show  good  lathering  properties,  and  asserts  that 
hardened  animal  and  vegetable  oils  after  careful  boiling  give  soaps 
which  not  only  are  harder  than  those  from  the  original  oil,  but  are 
essentially  whiter.  If  dark  soaps  have  been  produced,  one  perhaps 
can  explain  the  failure  on  the  ground  that  nickel  soaps  were  present 
in  the  hardened  oil  and  through  sulfur  compounds  in  the  lye  were 
converted  into  sulfide  of  nickel.  The  lack  of  lathering  qualities 
of  soap  made  from  hardened  fish  or  whale  oil  he  contends  is  a  per- 
fectly natural  result.  Hardened  fish  oil  finds  its  analogue  in  tallow. 
Pure  tallow  soaps  are  only  indifferently  soluble  and  lather  poorly; 
hence  this  condition  is  to  be  expected  in  hardened  fish  oil. 

Among  a  large  collection  of  samples  of  soaps  made  from  various 
hardened  oils,  including  many  marine  animal  oils,  some  were  found 
to  have  a  disagreeable  odor  like  oil  which  has  been  distilled.  This 
penetrating  odor,  which  in  distillation  plants  arises  through  partial 
decomposition  of  fatty  bodies,  is  regarded  as  due  to  acrolein  and  is 
not  a  necessary  consequence  of  hydrogenation,  but  is  simply  a  result 
of  over-heating  the  oil  at  some  time  during  Operation.  In  carrying 
out  the  process  technically,  too  high  a  temperature  should  be  avoided, 
thus  eliminating  the  disagreeable  odor  and  producing  a  hardened  oil 
from  which  soap  of  high  quality  may  be  prepared.  By  the  addition 
to  hardened  fish  or  vegetable  oil  of  other  fatty  material,  such  as  palm 

*  It  should  be  remembered  that  in  Germany  the  Leprince  and  Siveke  Patent 
141,029  is  generally  regarded  as  controlling,  and  is  in  strong  hands.  In  consequence 
the  criticism  of  hardened  oil  products  by  professional  circles  has  been  perhaps  unduly 
severe,  if  not  in  part  unwarranted. 

Haleco  (Seifen.  Ztg.  (1913),  16)  feels  that  the  stand  taken  by  Bergo  is  unwar- 
ranted, because  although  the  hardening  of  oils  on  a  large  scale  has  been  in  practical 
operation  for  only  a  short  period,  yet  in  that  time  there  has  been  a  Very  considerable 
demand  for  the  hardened  material,  which  demand  is  daily  increasing  in  the  soap 
industry  and  other  fields.  To-day  soaps  of  various  qualities,  including  fine  toilet 
soaps,  are  being  made  with  a  considerable  proportion  of  hardened  oil  which  shows 
that  the  new  material  offers  advantages. 


USES  OF  HYDROGENATED  OILS  373 

kernel  or  cocoanut  oil  and  rosin,  a  quick  lathering  soap  may  be  pre- 
pared which  satisfies  all  requirements. 

Hauser  *  is  of  the  view  that  the  application  of  hardened  oils  in  soap 
making  is  for  the  time  considerably  limited.  It  is  not  impossible 
that  a  considerable  simplification  of  the  apparatus  will  enable  the  soap 
manufacturers  to  make  use  of  it  more  extensively.  The  more  impor- 
tant applications,  to  Hauser,  appear  to  be  in  the  stearin  and  edible  fat 
industry.  He  regards  the  soaps  made  from  hardened  fat  as  lacking 
in  satisfactory  texture  and  emulsifying  properties,  as  not  exhibiting 
the  best  of  keeping  qualities  and  in  storage  sometimes  even  develop- 
ing an  undesirable  odor.  Then,  too,  he  considers  the  yield  of  glycer- 
ine to  be  unfavorably  affected  by  hydrogenation  and  the  fatty  acids 
of  hardened  oil  to  be  darker  than  those  of  the  normal  oil.  In  a  modern 
soap  establishment  it  is  recommended  that  cheap,  low-grade  fat  stock 
be  the  raw  material,  which,  after  purification,  is  split  and  the  result- 
ing fatty  acids  are  distilled  after  hardening  by  treatment  with  sulfuric 
acid.  In  this  way  with  great  simplicity  and  certainty,  according  to 
Hauser,  fractions  of  any  desired  titer  may  be  obtained  for  various 
soap  compositions  without  the  occurrence  of  undesirable  side  reac- 
tions which  he  apparently  thinks  are  unavoidable  in  hydrogenation 
processes. t 

In  the  stearin  industry  the  oil  may  be  hardened  and  then  saponified, 
or  the  glycerine  first  may  be  removed  and  the  fatty  acids  hardened. 
It  no  longer  becomes  necessary  to  employ  complicated  pressing  oper- 
ations to  separate  stearin  from  olein  as  the  stearin  may  be  di- 

*  Seifen.  Ztg.  (1913),  141. 

f  Favorable  comment  of  the  Germania  Oelwerke  products  is  made  by  "R.  D." 
(Seifen.  Ztg.  (1912),  517)  who  states  that  these  hardened  oils  have  many  technical 
uses.  In  soap  making  they  are  used  to  advantage  and  give  a  good  product.  Talgol 
and  Talgol  extra  are  used  as  entire  substitutes  for  tallow.  Talgol  is  best  for  common 
household  soaps,  Talgol  extra  for  toilet  soaps.  Candelite  and  Candelite  extra  on 
account  of  high  melting  point  find  advantageous  application  in  the  stearin  and 
candle  industry.  He  considers  the  odor  of  the  hardened  oils  as  slight  and  unob- 
jectionable. The  color  is  gray -yellow.  Soaps  made  from  these  correspond  to  the 
trade  requirements.  Toilet  soaps  have  a  pure  white  color  and  do  not  darken  or 
discolor  on  standing,  and  the  perfume  remains  intact.  Lower-grade  soaps  possess 
a  satisfactory  appearance,  lather  well  and  are  sufficiently  firm  and  the  odor  is  satis- 
factory. 

Considering  the  application  of  hardened  fat  in  soap  making  Schuck  (Soap 
Gazette  and  Perfumer,  1914,  55)  states  that  on  account  of  the  high  titer  of  the  fat 
it  is  not  advisable,  in  fact  well  nigh  impossible,  to  make  a  settled  soap  (without 
rosin)  from  the  hydrogenated  product  alone.  Such  a  soap  would  be  too  brittle, 
would  crack  and  would  not  lather  at  all. 

Train  oil  (hardened)  as  a  competitor  of  tallow  is  considered  in  Soap  Gazette  and 
Perfumer,  1913,  222.  See  also  article  by  Heller,  ibid.,  1913,  263. 


374 


THE  HYDROGENATION  OF  OILS 


rectly  obtained.     The  products  to  which  he  refers  have  the  following 
constants : 


Talgol 

Talgol  extra 

Candelite 

Candelite 
extra 

Iodine  number  
Melting  point  
Saponification  value  
Unsaponifiable  

65-70 
35-37°  C. 
192 
under  1% 

45-55 
42-45°  C. 
192 
under  1% 

15-20 
48-50°  C. 
192 
under  1% 

5-10 
50-52 
192 
under  1% 

Glycerine  content  

9-10% 

9-10 

9-10 

9-10 

A  polemical  article  by  Ribot*  denounces  the  proposal  to  use  har- 
dened fish  or  whale  oil,  no  matter  how  well  refined,  in  the  best  grade 
of  toilet  soaps.  Furthermore  he  does  not  consider  such  hardened 
oils  to  be  substitute  fats  for  tallow  or  palm  kernel  oil,  but  rather  that 
the  former  may  be  employed  as  addition  or  filling-in  fat  stock.  20  to 
25  per  cent  may  be  added  to  a  cheap  toilet  soap  base  without  detri- 
ment; 30  per  cent  or  even  40  per  cent  may  be  employed  in  laundry 
soaps.  In  white  soft  soaps  40  to  50  per  cent  of  Crutolin  may  be  used.f 
Schaal  t  apparently  is  in  agreement  with  Ribot  that  for  the  highest 
grade  of  toilet  soap  base,  tallow  should  not  be  materially  reduced  or 
displaced  by  Talgol,  but  maintains  that  a  soap  base  may  be  prepared 
with  35  to  40  per  cent  of  Talgol  which  yields  a  handsome  milled  soap 
permanent  in  quality  and  suffering  no  eventual  change  in  color.  He 
also  asserts  that  for  ordinary  toilet  soap  base  Talgol  is  in  no  sense  an 
addition  or  filling-in  fat,  but  is  a  real  substitute  for  tallow,  and  that 
the  same  is  true  of  Talgol  extra  and  Candelite  respectively  for  shaving 
soaps  and  glycerine  transparent  soaps;  further  that  the  hydrogen- 
ation  process  is  an  important  and  fruitful  discovery  for  the  soap 
industry,  especially  for  toilet  soap  manufacture. 

In  "Eschweger"  soaps  tallow  may  be  completely  replaced  by  Tal- 
gol,! which  produces  a  firmer  soap;  the  yield  is  good  and  the  odor 
satisfactory  and  no  objection  has  been  raised  to  its  lathering  qualities. 

*  Seifen.  Ztg.  (1913),  142. 

t  In  response  to  Ribot  an  article  appeared  in  Seifensieder  Zeitung  (1913),  173, 
by  Schaal  in  which  the  latter  makes  clear  that  he  did  not  propose  hydrogenated 
fish  or  whale  oil  of  the  Talgol  type  for  making  the  very  highest  grade  of  soap  base; 
he  recommends  such  fats  particularly  for  toilet  soaps  of  medium  quality.  Schaal 
also  states  that  he  has  never  recommended  complete  substitution  of  tallow  by  Talgol 
fat  in  the  highest  grade  of  toilet  soap  base  and  calls  attention  to  the  formulae  which 
he  has  published  in  the  past  in  which  a  substantial  amount  of  tallow  is  specified. 

t  Seifen.  Ztg.  (1913),  173. 

§  Seifen.  Ztg.  (1912),  1230. 


USES  OF  HYDROGENATED  OILS  375 

Two  formulae  are  given  for  filled  Eschweger  soap  according  to  which 
a  firm  marbled  product  is  obtained.* 

Transparent  glycerine  soaps  may  be  prepared  by  the  use  of  a  hard 
variety  of  hardened  oil,  Candelite  being  especially  suitable,  and  with 
this  material  a  soap  of  very  satisfactory  transparent  appearance  and 
firm  consistency  may  be  prepared  without  using  more  than  a  normal 
amount  of  alcohol.  The  following  are  suitable  formulas  for  the  prep- 
aration of  such  soaps: 

Cheap  Grade 

90  kilos  Candelite. 

90  kilos  Ceylon  cocoanut  oil. 

84  kilos  castor  oil. 
144  kilos  caustic  soda  lye,  38°  Be". 

90  kilos  sugar  dissolved  in  an  equal  weight  of  water. 
100  kilos  soap  filling. 

30  kilos  soda  crystals. 
Alcohol  q.s. 

The  soap  filling  consists  of  100  parts  salt,  140  parts  potash,  40  parts 
sugar  and  sufficient  water  to  produce  a  solution  of  21°  Be. 

Better  Grade 

90  kilos  Candelite. 
120  kilos  Ceylon  cocoanut  oil. 

90  kilos  castor  oil. 
166  kilos  caustic  soda  lye,  38°  Be*. 
100  kilos  sugar  dissolved  in  75  kilos  of  water. 

40  kilos  soap  filling. 

10  kilos  glycerine. 
Alcohol  q.s. 

The  Candelite  should  first  be  melted,  the  cocoanut  oil  then  added 
and  finally  the  castor  oil  introduced.  Saponification  is  carried  out 
by  the  self-heating  method,  it  being  desirable  to  allow  the  saponified 
mass  to  stand  an  hour  or  so  in  order  to  assure  a  complete  union  of  the 

*  "Eschweger"  is  a  marbled  soap,  made  by  saponifying  tallow  and  soft  fats 
together  with  about  one-third  of  their  weight,  or  more,  of  cocoanut  oil.  The  quan- 
tity of  lye  is  gauged  so  as  to  have  the  soap  very  nearly  neutral  at  the  end  of  the 
operation,  as  there  is  no  separation  of  waste  lye.  All  that  goes  into  the  kettle  also 
goes  into  the  soap  except  of  course  water  removed  by  evaporation.  Owing  to 
the  properties  of  cocoanut  oil,  such  soap,  in  absorbing  a  considerable  amount  of 
salt  solution,  becomes  of  a  peculiar  consistency,  while  hot,  and  crystallization  ensues 
with  the  formation  of  "marble"  or  "mottle"  on  cooling  in  the  frame.  At  the  same 
time  the  soap  holds  much  more  water  than  one  which  has  been  mottled  by  boiling 
down  a  soap  made  entirely  of  soft  fats. 


376  THE  HYDROGENATION  OF  OILS 

ingredients.  Then  the  sugar  solution  and  filling  are  added.  By 
proceeding  in  this  manner  a  clear  product  is  obtained  which  does  not 
subsequently  darken  in  storage.  The  amount  of  alcohol  is  usually 
about  3  to  4  per  cent,  calculated  on  the  soap  material.  For  the  better 
quality  a  very  satisfactory  perfuming  composition  is  obtained  by 
mixing  equal  parts  of  "  palma  rosa  "  oil  and  artificial  geranium  oil 
using  1500  grams  to  the  formula  given  above.  For  the  cheaper  grade 
of  soap  a  good  perfuming  agent  consists  of  a  mixture  of  equal  parts  of 
Java  citronella  oil  and  benzyl  acetate.  2000  grams  of  this  mixture 
should  be  used  for  the  amount  of  material  specified  in  the  formula 
first  above  given.* 

Hardened  oil  is  advantageously  used  in  shaving  soaps  according 
to  Schaal.f  A  formula  given  by  him  is  the  following: 

50  kilos  Talgol  extra. 

10  kilos  Ceylon  cocoanut  oil. 

10  kilos  lard. 

20  kilos  caustic  soda  lye,  38°  Be". 

21  kilos  caustic  potash  lye,  37°  B6. 

The  mixing  takes  place  at  a  temperature  of  52°  C.  The  lyes  are 
first  mixed  and  then  added  in  a  thin  even  stream,  stirring  well  mean- 
while in  order  to  quickly  get  a  thorough  incorporation.  After  |  to  f 
hour  the  batch  stirs  thickly  and  should  be  promptly  framed.  The 
mass  heats  strongly  in  the  frames  and  to  take  advantage  of  this  the 
frames  should  be  covered  with  bagging.  By  such  treatment  a  section 
of  the  soap  will  show  a  uniform  texture  from  center  to  edge. 

If  it  is  preferred  to  prepare  this  soap  by  the  warm  process,  it  is 
necessary  to  add  5  kilos  of  potash  solution  of  12°  B£.  to  the  caustic 
lyes  and  to  prolong  the  stirring  until  the  mass  has  the  proper  body; 
the  kettle  is  then  well  covered  and  its  contents  given  time  to  react. 
After  2  to  3  hours  spontaneous  heating  will  have  set  in.  The  kettle 
is  again  opened,  the  contents  well  crutched,  until  uniform,  and  at  the 
same  time  perfume  can  be  worked  in.  The  soap  is  now  ready  for 
framing,  but  the  frames  need  not  be  covered.  The  potash  solution 
is  added  to  keep  the  soap  sufficiently  fluid  to  permit  of  crutching. 
Without  this  addition  the  soap  would  be  so  solid  and  tenacious  that 
the  crutch  could  scarcely  operate.  The  finished  soap  has  a  flawless 
appearance,  is  almost  white,  fairly  solid  and  handles  well  in  cutting 
and  packing. 

*  Schaal,  Seifen.  Ztg.  (1912),  955. 

t  Seifen.  Ztg.  (1912),  954,  and  Die  Moderne  Toiletteseifen-Fabrikation. 


USES  OF  HYDROGENATED  OILS  377 

A  perfume  composition  which  may  be  employed  in  this  soap  con- 
sists of  the  following: 

200  grams  oil  of  rosemary. 

200  grams  oil  of  bitter  almonds  (artificial). 

150  grams  oil  of  lavender. 

75  grams  oil  of  thyme  (white). 
100  grams  oil  of  sassafras. 

25  grams  oil  of  wintergreen  (artificial). 

The  odor  and  lathering  properties  of  soaps  made  from  hydrogen- 
ated  oil  are  discussed  by  Garth  *  who  considers  the  characteristic 
odor  of  hardened  oils  of  the  Talgol  type  to  be  in  nowise  disagree- 
able. In  laundry  soaps  the  aromatic  odor  of  the  rosin  overcomes  the 
Talgol  smell.  In  making  toilet  soaps  one  has  to  take  greater  care 
that  the  Talgol  addition  is  well  gauged  as  otherwise  the  proportion 
of  the  customary  perfuming  agents  has  to  be  varied.  With  regard 
to  the  diminution  of  the  lathering  power  he  states  that  soaps  from 
pure  Talgol  have  almost  no  lather,  and  in  this  connection  refers  to 
the  interesting  work  of  Krafft  and  other  investigators  who  have  shown 
that  the  detergent  action  of  soap  is  dependent  upon  the  nature  of  the 
fatty  acid,  and  that  there  exists  an  important  difference  in  operation 
between  stearin  and  olein  soaps.  Soaps  from  palmitin  or  stearin 
at  common  temperature  are  unworkable  and  develop  their  detergent 
or  emulsion-forming  properties  only  when  a  temperature  is  reached 
which  is  approximately  that  of  the  melting  point  of  their  fatty  acids. 
On  the  other  hand  the  olein  soaps  are  soluble  at  ordinary  temper- 
atures thus  exerting  detergent  action  at  low  temperatures,  but  at  a 
temperature  of  about  80°  C.  they  lose  their  emulsion-forming  qualities. 
Thus  it  will  be  seen  why  soaps  made  from  pure  tallow,  or  hardened 
fat,  exert  a  very  slight  detergent  action  at  ordinary  temperature.  In 
working  with  hardened  fat  the  soap  expert  should  take  cognizance 
of  the  manner  in  which  the  soap  is  to  be  used  and  employ  such  mate- 
rials as  give  the  desired  detergent  property  under  these  conditions. 

With  30  to  35  per  cent  of  hydrogenated  oil  of  the  Talgol  type, 
Weber  f  has  made  a  satisfactory  soap  base  holding  its  perfume  well, 
and  although  prepared  without  special  manipulation  did  not,  after 
standing  for  half  a  year,  show  the  hardened  oil  odor  when  broken. 
This  interval  of  time  is  sufficient  to  determine  with  certainty  whether 
or  not  the  characteristic  odor  can  be  permanently  suppressed. 

The  fatty  acids  of  hydrogenated  oil  have  been  examined  by  Luksck  { 

*  Seifen.  Ztg.  (1912),  1309. 

t  Seifen.  Ztg.  (1913),  421. 

J  Seifen.  Ztg.  (1912),  718  and  742. 


378  THE  HYDROGENATION  OF  OILS 

with  reference  to  their  applicability  as  candle  material.  A  product 
having  a  titer  of  about  60  was  observed  to  have  a  greasy  feel,  to  be  of 
amorphous  texture  and  to  be  lacking  in  ring  and  transparency.  So 
far  as  the  samples  examined  by  Luksch  are  concerned  the  product  does 
not  appear  to  be  suitable  as  a  candle  material  without  considerable 
compounding.* 

In  saponifying  for  fatty  acids  it  is  not  advisable  to  run  above  92  per 
cent,  as  otherwise  the  fatty  acids  are  likely  to  be  dark  and  the  result- 
ing soap  off  color.  When  hydrogenated  fish  oil  has  been  split  the  fatty 
acids  are  saponified  in  the  customary  way  by  carbonated  alkali. 
In  finishing,  the  soap  should  not  be  too  thin;  otherwise,  in  spite  of 
the  high  melting  point  of  the  hardened  fat,  the  soap  will  be  soft. 
The  soap  should  be  separated  only  with  an  excess  of  lye.  It  separates 
rather  badly  and  should  be  allowed  to  stand  two  or  three  days  in  the 
kettle  in  order  to  harden.  A  soap  made  from  Talgol  with  30  per  cent 
of  rosin  is  of  fair  appearance,  lacking,  however,  the  transparency  of 
soap  prepared  with  a  large  content  of  palm  kernel  oil.  While  the  color 
is  good,  there  is  a  noticeable  dullness  of  surface.  After  drying  and 
pressing  it  acquires  a  satisfactory  glossy  finish.  While  a  soap  made 
only  from  hardened  fish  or  whale  oil  has  practically  no  lathering  prop- 
erties, the  addition  of  30  per  cent  of  rosin  greatly  improves  this  defect 
and  very  good  lathering  properties  result,  f 

*  Even  if  it  were  possible,  "J.  G."  states  (Seifen.  Ztg.  (1912),  1146),  to  split  the 
fat  completely  on  a  commercial  scale,  the  color  of  the  fatty  acids  excludes  the  direct 
application  of  the  product  in  candle  manufacture.  He  even  claims  that  it  is  neces- 
sary to  subject  the  saponified  product  either  to  distillation  or  to  pressing,  and  that 
in  the  latter  case  the  poor  crystallization  of  the  fatty  acids  gives  rise  to  difficulties. 
But  he  adds  that  the  ordinary  stearin  candle  is  made  up  largely  of  a  mixture  of 
palmitic  and  stearic  acid  in  which  a  certain  ratio  between  the  two  fatty  acids  must 
exist  to  maintain  the  quality  of  the  candle.  Hence  in  judging  hardened  fat  with 
reference  to  its  application  as  a  candle  material,  the  composition  of  the  original 
fat  is  not  unimportant,  for  useful  mixtures  may  well  be  obtained  through  careful 
selection  of  the  raw  materials.  In  those  cases  where  the  nature  of  the  chemical 
individuals  derived  by  hydrogenation  have  not  been  entirely  made  clear,  as  in  the 
case  of  fish  and  whale  oil,  further  practical  investigations  will  be  necessary  to  show 
whether  or  not  hydrogenation  will  afford  a  generally  useful  product  in  candle  manu- 
facture. 

t  Seifen.  Ztg.  (1912),  870. 

A  few  years  hence  when  oil  hydrogenation  has  found  its  measure  and  the  more 
important  points  concerning  it  have  reached  definite  settlement,  the  allotment  of 
space  to  a  number  of  the  discussions  appearing  in  this  chapter  hardly  would  be 
warranted,  but  at  the  present  time  when  many  are  desirous  of  having  at  hand  a 
review  which  comprises  all  or  nearly  all  the  published  work  to  date,  containing 
though  it  does  a  considerable  divergency  of  opinion,  there  appears  ample  justification 
for  the  inclusion  of  such  discussions  as  those  given  above. 


USES  OF  HYDROGENATED  OILS  379 

A  tallow-like  product  which  has  been  brought  into  the  market  as 
"  Talgit "  is  prepared  by  hydrogenating  fish  or  whale  oil.  Mullet 
has  examined  this  product  *  and  has  reported  the  acid  number  as  12.8 
and  the  iodine  number  as  49.  The  fatty  acids  exhibited  a  titer  of 
39.4°  C.  When  Muller  attempted  to  saponify  the  fat  by  the  Twitchell 
process,  dark  colored  fatty  acids  were  produced,  caused,  it  is  supposed, 
by  oxidation  during  saponification.  Muller  observes  that  copper, 
iron  and  lead  tend  to  cause  a  discoloration  of  fat  which  is  treated  by 
the  Twitchell  process,  and  he  concludes  that  the  traces  of  nickel  which 
were  present  in  Talgit  acted  in  a  similar  manner.  When  he  subjected 
the  fat  to  cleavage  by  the  autoclave  process  very  light  colored  fatty 
acids  were  obtained.  A  pressure  of  10  to  11  atmospheres  was  main- 
tained in  the  autoclave  for  a  period  of  8  hours  and  the  resulting  fatty 
acids  were  found  to  contain  about  2.5  per  cent  of  unsaponified  fat. 
The  following  results  were  obtained  from  an  examination  of  the  fatty 
acids: 

Acid  number  of  the  fatty  acids 194 . 0 

Saponification  value  of  the  fatty  acids 198 . 0 

Titer 39 . 2°  C. 

Acid  number  of  the  liquid  fatty  acids 186 . 3 

Saponification  values  of  the  liquid  fatty  acids 191 . 2 

Iodine  number  of  the  liquid  fatty  acids 100 . 0 

Titer  of  the  liquid  fatty  acids 14 . 3°  C. 

Titer  of  the  solid  fatty  acids 48 . 7°  C. 

The  fatty  products  of  the  saponification  pressed  very  readily  and 
about  35  per  cent  of  solid  fatty  acids  were  obtained  whose  low  titer 
(48.7°  C.)  indicates,  according  to  Muller,  that  fatty  acids  in  addition 
to  or  other  than  stearic  and  palmitic  acids  are  present,  for  the  solidify- 
ing point  of  mixtures  of  palmitic  and  stearic  acids  is  above  53.5°  C. 
The  presence  of  iso-oleic  acid  which  causes  a  lowering  of  the  titer  of 
stearic  acid  obtained  by  distillation  is  not  to  be  expected  in  this  case, 
but  Muller  has  not  further  investigated  the  acid  mixture  to  identify 
any  of  its  components.  As  the  fatty  acids  pressed  satisfactorily, 
Muller  concludes  that  the  stearic  acid  was  technically  pure,  hence  the 
low  titer  cannot  be  ascribed  to  the  presence  of  undue  amounts  of 
liquid  fatty  acids.  The  expressed  fatty  acids,  or  oleic  acid,  obtained 
as  stated  above,  exhibited  a  straw  yellow  color  and  showed  the  char- 
acteristic odor  of  hardened  fish  or  whale  oil.  Muller  states  that  for 
many  purposes  the  iodine  number  of  these  liquid  fatty  acids  is  too 
high.  He  concludes  that  so  far  as  this  product  is  concerned  the  hydro- 
genation  of  the  unsaturated  fatty  acids  does  not  proceed  successively 

*  Seifen.  Ztg.  (1913),  1376. 


380  THE  HYDROGENATION  OF  OILS 

so  as  to  convert  all  of  the  unsaturated  bodies  having  two  or  more 
double  bonds  into  bodies  having  only  one  double  bond  before  the 
latter  bodies  are  hydrogenated,  or  in  other  words  that  linoleic  and 
linolenic  acids  are  not  all  converted  into  oleic  acid  before  stearic 
acid  forms,  but  instead  of  this  that  reduction  takes  place  throughout, 
so  that  all  types  of  unsaturated  compounds  are  more  or  less  reduced 
simultaneously.  This  observation  is  of  interest  because,  as  Mliller 
notes,  the  presence  of  highly-unsaturated  bodies  of  the  nature  of  dry- 
ing oils  in  such  products  is  often  undesirable. 

Mtiller  prepared  soap  from  Talgit  and  found  it  to  have  little  or  no 
detergent  and  lathering  properties  which  he  notes  is  to  be  expected 
with  fats  of  this  titer,  and  in  consequence  of  these  properties,  prod- 
ucts of  the  nature  of  Talgit  cannot  be  used  as  the  essential  fat  mate- 
rial, but  should  be  used  only  as  additions  to  the  main  fat  stock. 

Commenting  on  the  observation  of  Miiller  regarding  the  properties  of  Talgit, 
Dubovitz  (Seifen.  Ztg.  (1913),  1445)  notes  that  the  investigation  of  the  fatty  acids 
of  hardened  fish  oil  indicates  that  there  is  present  an  acid  whose  molecular  weight 
is  less  than  that  of  palmitic  acid.  Also  it  is  stated  that  it  is  possible  to  obtain  stearic 
acid  or  stearin  having  a  titer  of  53  to  55  degrees  from  strongly  hardened  fish  oil 
simply  by  pressing. 

Miiller  (Seifen.  Ztg.  (1914),  8)  discusses  the  comments  of  Dubovitz  and  points 
out  that  mixtures  of  two  saturated  fatty  acids  crystallize  well  from  the  stearin 
manufacturer's  point  of  view,  while  mixtures  of  three  or  more  fatty  acids  as  a  rule 
produce  an  amorphous  mass. 

The  contention  of  Dubovitz  that  the  low  titer  of  stearin  can  be  explained  by 
the  presence  of  saturated  fatty  acids  with  less  than  16  carbon  atoms  in  the  molecule 
and  derived  from  the  corresponding  unsaturated  compounds  by  hydrogenation 
rests  on  the  assumption  of  the  existence  of  just  such  unsaturated  fatty  acids,  or 
their  glycerides,  in  fish  oils.  Proof  of  this  is  said  to  be  lacking  up  to  the  present. 
Even  the  presence  of  hypogeic  and  physetoleic  acids  in  these  oils  is  still  doubted. 
It  is  held  that  the  low  titer  of  the  stearin  in  question  was  due  to  the  presence  of 
unsaturated  fatty  acids.  (Seifen.  Ztg.  (1914),  33.) 

In  discussing  the  distillation  of  fatty  acids,  Hajek*  states  that 
some  difficulties  are  encountered  when  working  up  hydrogenated  oils 
to  produce  fatty  acids.  He  states  that  all  fats  which  are  treated  when 
hot  with  air  or  other  gases  for  a  considerable  length  of  time,  after  auto- 
clave saponification,  yield  dark  colored  fatty  acids  and  that  this  dis- 
coloration is  due  to  a  chemical  change  which  takes  place  in  coloring 
agents  present,  similar  in  character  to  that  which  occurs  in  the  distil- 
lation of  fatty  acids  at  elevated  temperatures,  or  with  an  insufficient 
proportion  of  superheated  steam,  f 

*  Seifen.  Ztg.  (1913),  445. 

f  The  idea  which  has  been  entertained  that  hardened  triglycerides  could  be  directly 
used  for  candle  material  is  out  of  question,  as  no  one  would  care  to  inhale  the  vapors 


USES  OF  HYDROGENATED  OILS  381 

Norrnann  has  made  candles  with  stock  obtained  from  hardened  fish 
or  whale  oil  which  burned  brightly  and  without  odor,  similar  to  the 
best  grade  of  stearin  candles.* 

The  properties  of  hardened  castor  oil  have  been  noted  by  Garth. f 
As  is  generally  known,  castor  oil  differs  in  many  respects  from  other 
common  oils  in  such  respects  as  its  high  viscosity,  solubility  in  alcohol 
and  difficulty  of  salting  out  its  soaps  by  electrolytes.  The  constants 
of  one  sample  examined  by  Garth  are  as  follows: 

Acid  number 3.5 

Saponification  number 183 . 5 

Iodine  number 4.8 

Acetyl  number 153 . 5 

Acetyl  number  of  the  fatty  acids 143 . 1 

Acid  number  of  the  fatty  acids 184 . 5 

Saponification  number  of  the  fatty  acids 187 . 9 

Melting  point  of  the  fat 68°  C. 

Melting  point  of  the  fatty  acids 70°  C. 

Melting  point  of  the  acetylated  acids 47°  C. 

These  results  indicate  that  the  Saponification  and  acetyl  number 
do  not  change.  The  difference  between  the  acid  number  of  the  fatty 
acids  and  their  Saponification  number  points  to  the  formation  of 
lactones. 

From  the  point  of  view  of  soap  technics,  it  may  be  noted  that  the 
hardened  product  saponifies  with  dilute  lye  about  as  easily  as  common 

coming  from  candles  in  which  acrolein  was  being  generated.  Any  large  proportion 
of  nickel  in  the  fat  would  also  interfere  with  the  burning  qualities.  (Sach,  Zeitsch. 
f.  angew.  Chem.,  1913,  No.  94,  784.) 

The  slight  lathering  properties  of  soap  made  from  hardened  tran  is  to  be  expected, 
because  this  fat  finds  its  analogue  in  tallow.  Pure  tallow  soaps  are  very  difficultly- 
soluble  and  lather  very  poorly  so  the  same  property  may  be  looked  for  in  hardened 
fish  oil  or  whale  oil.  (Seifen.  Ztg.  (1912),  1003.) 

The  dark  colored  soaps  which  have  been  noted  by  some  users  of  hardened  oil 
may  be  due  to  traces  of  nickel  soap  in  the  oil  which  react  with  sulfur  compounds 
in  the  lye,  resulting  in  the  formation  of  nickel  sulfide  and  consequent  discoloration. 
(Seifen.  Ztg.  (1912),  1003.) 

The  odor  of  hardened  tran  is  very  much  like  that  of  distilled  oils  and  recalls 
the  penetrating  disagreeable  odor  which  is  observed  in  distillation  works  and  which 
is  apparently  due  to  the  partial  decomposition  of  fatty  acids  with  the  production 
of  acrolein  bodies.  Odors  of  this  character  materially  affect  the  quality  of  the  soap, 
but  this  trouble  may  be  avoided  if  greater  care  is  taken  in  the  hardening  process  to 
avoid  over-heating  of  the  oil  or  fat.  By  skillful  working  at  not  too  high  a  temper- 
ature, the  disagreeable  odor  does  not  appear  and  the  tran  is  rendered  completely 
odorless.  From  this  product  a  soap  may  be  made  which  is  beyond  criticism. 

*  Seifen.  Ztg.  (1914),  263. 

t  Seifen.  Ztg.  (1912),  1309. 


382  THE  HYDROGENATION  OF  OILS 

castor  oil.  Further,  soap  prepared  from  the  hardened  product,  in 
spite  of  its  high  melting  point,  like  castor  oil  soap,  has  a  similar  lack 
of  sensitiveness  against  salt  solutions  and  behaves  in  this  respect 
like  the  fats  of  the  cocoanut  oil  group.  Like  the  fats  of  the  latter 
group,  the  hardened  fat  may  be  saponified  at  a  temperature  of  about 
80°  to  90°  C.  While  a  soap  with  30  per  cent  fat  content  made  from 
ordinary  castor  oil  is  liquid,  the  corresponding  soap  from  hardened 
castor  oil  is  very  firm,  but  the  latter  soap  does  not  possess  the  prop- 
erty of  lathering  in  the  least. 

With  regard  to  tariff  rating  on  hardened  oil  Bohm  *  thinks  beyond 
question  the  hydrogenated  product  should  not  be  declared  and  rated 
like  the  untreated  oil  and  draws  an  analogy  between  raw  oils  and 
their  hydrogenated  products  and  formaldehyde  or  acetaldehyde  which 
yield  chemically  different  bodies,  respectively  methyl  and  ethyl  alcohol, 
by  taking  up  hydrogen. 

It  is  contended  f  that  Bohm's  illustrative  use  of  formaldehyde, 
which  body  through  the  addition  of  two  atoms  of  hydrogen  is  trans- 
formed into  methyl  alcohol  and  thus  into  an  essentially  different 
body  from  the  tariff  point  of  view,  is  not  entirely  analogous  with 
respect  to  hardened  oils,  for  oils  are  not  unitary  chemical  individuals, 
but  are  mixtures  of  triglycerides  of  various  fatty  acids.  Also  it  is 
held  that  hydrogenated  oils  are  not  essentially  single  chemical  individ- 
uals like  tristearin,  but  are  mixtures  of  various  fatty  acid  triglycerides 
in  which  mixtures,  of  course,  tristearin  is  present  in  much  greater 
quantities  than  in  the  original  oil.  A  differentiation  for  tariff  pur- 
poses on  the  ground  of  chemical  composition  is  thus  practically  im- 
possible.t 

Dr.  Bela  Lach,  in  the  Seifen.  Ztg.  (1912),  1245,  discusses  American  soap  manu- 
facture and  refers  to  the  Fels  Naptha  Soap  Works  of  Philadelphia,  as  being  users 
of  hydrogenated  oil.  He  says  that  Fels  Naptha  soap  contains  from  10  to  15  per  cent 
of  benzene  of  high  boiling  point,  and  that  the  raw  materials  are  in  a  large  part  cotton 
and  corn  oil.  Only  a  relatively  small  proportion  of  hard  stock,  such  as  tallow  or 

*  Seifen.  Ztg.  (1912),  738. 

f  Seifen.  Ztg.  (1912),  1003. 

t  An  article  by  Harmsen  (Seifen.  Ztg.  (1913),  638-39  and  661-62)  discusses  the 
matter  of  tariff  adjustment  of  hardened  fats,  and  he  states  that  by  the  hardening 
operation  the  consistency  and  other  qualities  of  the  oil  are  so  modified  that  a  recog- 
nition of  its  origin  is  in  most  cases  impossible  either  by  taste,  smell  or  chemical 
test.  Chemical  analysis  can  determine  only  whether  the  fat  is  of  animal  or  vegetable 
origin.  The  Hamburg  authorities  have  arrived  at  the  conclusion  that  hardened 
fat  or  oil  must  be  taxed  according  to  the  properties  and  quality  acquired  by  harden- 
ing. Harmsen  also  discusses  the  position  of  Talgol  from  the  tariff  standpoint  in 
Seifensieder  Zeitung  (1913),  745. 


USES  OF  HYDROGENATED  OILS  383 

palm  kernel  oil,  is  used.  The  amount  of  this  material  employed  is,  however,  reduced 
because  this  concern  has  been  able  to  make  use  of  hydrogcnated  oil,  a  material 
which  they  have  thoroughly  tested.  At  this  plant  Lach  states  he  saw  samples  of 
hardened  cotton  and  corn  oil,  as  well  as  various  kinds  of  hardened  fish  oil  which 
were  of  a  remarkably  fine  character.  They  had  the  hardness  and  appearance  of 
fine  tallow,  were  beyond  criticism  as  to  odor  and  could  be  worked  up  into  a  soap  in 
a  satisfactory  manner. 

A  hardened  oil  of  relatively  low  titer,  bearing  the  trade  name  of  "Krutolin"  (or 
Crutolin),*  is  discussed  in  the  Seifensieder  Zeitung  (1913),  930  and  954,  and  as  some 
of  the  observations  may  be  of  use  in  the  handling  of  other  more  or  less  similar  hydro- 
genated  products  the  following  data  is  here  included. 

On  account  of  the  great  demand  for  good  fats  and  oils  in  edible-fat  manufacture, 
the  prices  of  these  have  increased  very  materially,  and  it  has  become  continually 
more  difficult  to  obtain  fats  which  remain  white  on  boiling.  Therefore  hardened 
oils  such  as  Krutolin,  which  may  be  obtained  of  uniformly  good  quality,  promise 
to  be  of  decided  utility.  It  is  said  that  Krutolin  has  the  advantage  of  being  cheaper 
than  lard  and  cottonseed  oil,  and  that  in  addition  it  is,  as  has  been  proven  by  long- 
continued  experiments,  a  good  substitute  for  lard  and  white  cottonseed  oil.  When 
used  for  barrel  soaps,  Krutolin,  alone,  has  a  tendency  to  form  sirupy,  stringy  soaps. 
Therefore,  it  is  desirable  to  supplement  it  by  the  proper  addition  of  other  fats.  In 
practice  it  has  been  shown  that  the  danger  of  "lengthening"  of  unfitted  white  soft 
soaps  is  greater  than  when  more  or  less  potato  flour  is  used  as  a  filler.  Hence  it  is 
recommended  that  the  percentage  of  Krutolin  employed  be  kept  somewhat  lower 
for  such  unfilled  products. 

As  mutton  tallow,  cottonseed  oil,  peanut  oil  and  lard,  or  their  fatty  acids,  in  Ger- 
many are  the  usual  or  principal  raw  materials  for  white  soft  soap,  it  is  stated  that 
under  present  market  conditions  a  considerable  saving  is  attained  in  the  manufac- 
ture of  soaps  if  these  fats  are  replaced,  even  only  in  part,  by  Krutolin.  In  combi- 
nation with  the  above-named  raw  materials  Krutolin  furnishes  a  very  white  soap  for 
both  unfilled  or  filled  goods.  It  is  self-evident  that  a  primary  condition  for  the 
production  of  a  totally  white  soap  is  cleanliness  of  working.  Furthermore,  it  is 
necessary  to  pay  attention  to  the  alkali  and  especially  the  potato  flour  as  these  are 
often  of  varying  origin,  and  are  not  always  suitable.  Many  50-degree  caustic 
potash  lyes  give  perfectly  water-white  solutions  when  diluted;  others,  however,  show 
a  yellow  tone.  With  filled  soaps  the  quality  of  the  potato  flour  has  a  strong  influ- 
ence on  the  character  of  the  finished  product.  Every  shipment  should  be  tested 
for  color  and  to  ascertain  whether  the  flour  has  been  treated  with  acid.  Potato 
flours  containing  acid  are  to  be  excluded  for  filling  white  soft  soaps,  as  they  produce 
an  after-darkening.  The  kind  of  water  used  also  has  some  influence  on  the  color 
of  these  soaps. 

A  stock  for  unfilled  figged  soap  containing  Krutolin  follows: 

1500  kg.  mutton  tallow 

900  kg.  cottonseed  oil 

600  kg.  Krutolin 
3000kg. 

On  account  of  the  high  titer  which  mutton  tallow  possesses  and  in  recognition 
of  the  fact  that  Krutolin  easily  favors  the  "lengthening"  of  the  soap,  one  must 

*  Krutolin  is  stated  to  be  a  substitute  for  "technical"  lard  and  American  cotton 
oil  (Seifen.  Ztg.  (1913),  1386). 


384  THE  HYDROGENATION  OF  OILS 

from  the  beginning  count  on  a  strong  increase  of  carbonated  alkali  to  reduce  the 
causticity  of  the  caustic  potash  lye.  It  is  possible,  in  the  above  stock,  to  use  30  kg. 
96  to  98  per  cent  potash  to  100  kg.  of  50-degree  caustic  potash  lye.  It  will  often 
be  advisable,  especially  during  the  warm  season,  to  substitute  ammonia  soda  solu- 
tion for  a  part  of  the  potash  solution,  in  order  to  secure  an  easy  and  rapid  figging  of 
the  soap. 

After  completion  of  the  boiling,  samples  are  to  be  carefully  tested  to  ascertain 
if  the  soap  has  been  sufficiently  shortened  by  carbonated  alkali.  Samples  placed 
on  glass  must  remain  liquid  a  long  time,  and  on  stirring  after  cooling  must  not  show 
any  stringiness.  Should  the  soap  still  remain  tough  and  gum-like  a  later  addition 
of  concentrated  potash  or  soda  solution  is  necessary  in  order  to  produce  a  satisfac- 
tory product.  On  account  of  the  large  amount  of  carbonated  alkali  which  can  be 
absorbed,  the  yield  of  this  soap  is  very  good. 

The  mutton  tallow  can  be  omitted  and  a  somewhat  larger  amount  of  white  lard 
substituted.  The  composition  would  then  be  about  as  follows: 

1600  kg.  lard 
750  kg.  cottonseed  oil 
650  kg.  Krutolin 
3000kg. 

As  lard  has  a  considerably  lower  titer  than  mutton  tallow,  the  amount  of  shorten- 
ing material  used  with  this  stock  must  be  decreased  accordingly.     With  the  stock 
first  given,  which  contained  a  large  amount  of  mutton  tallow,  additions  of  caustic 
soda  lye  were  not  necessary,  but  in  this  case,  where  softer  fats  form  the  basis,  it  is 
advisable  to  add  about  20  per  cent  of  caustic  soda  lye  in  the  boiling.     The  neutral 
fats  in  this  stock  can  be  replaced  by  fatty  acids,  but  as  soaps  from  neutral  fats  are 
whiter,  this  is  not  to  be  recommended.     A  moderate  filling  with  flour  is  advanta- 
geous when  using  fatty  acid  stock.     A  figged  soap  with  a  little  filling  can  hardly  be 
distinguished  by  visual  examination  from  one  which  is  unfilled.     For  the  above 
stock  of  3000  kg.  the  following  filler  is  recommended: 
300  kg.  best  potato  flour. 
600  kg.  12-degree  potash  solution. 
300  kg.  lye,  30°  Be*. 

The  filler  is  to  be  added  in  the  morning  if  the  soap  has  cooled  sufficiently  over  night. 
The  soap  is  perfumed  with  sal-ammoniac,  turpentine,  safrol,  oil  of  camphor,  lemon 
oil  or  suitable  mixtures  of  these. 

For  a  first-class  "sal-ammoniac-turpentine"  soft  soap,  where  particular  value  is 
laid  upon  the  resulting  white  color,  and  less  on  the  figged  effect,  mutton  tallow  and 
cottonseed  oil  may  be  left  out  and  Candelite  and  Talgol  substituted  in  part  therefor. 
The  composition  would  then  be  the  following: 

2000  kg.  Krutolin. 

1000  kg.  Candelite. 

For  the  reduction  of  the  causticity  30  kg.  potash  should  be  used  to  every  100  kg. 
50-degree  caustic  potash  lye.  On  boiling  about  one-third  caustic  soda  is  to  be  added. 
To  the  latter  25  kg.  ammonia  soda  are  added  to  every  100  kg.  soda.  These  alkalies 
are  dissolved  separately,  mixed  and  the  lye  diluted  to  the  required  strength. 

The  above  stock  gives  a  soap  of  special  toughness.  Therefore,  it  may  be  neces- 
sary to  add  more  or  less  soda  or  potash  solution  according  to  the  result  of  tests  made 
from  time  to  time,  until  the  soap  possesses  the  desired  normal  characteristics.  "Sal- 
ammoniac  turpentine  soap"  made  according  to  this  formula  possesses  a  very  white 


USES  OF  HYDROGENATED  OILS  385 

color  and  by  use  of  first-class  potato  flour  can  be  filled  up  to  25  per  cent  without 
influencing  the  color. 

The  filler  is  made  up  as  previously  mentioned,  but  must  have  an  addition  of 
potash  filler.  Its  make-up  thus  becomes: 

750  kg.  potato  flour. 
1500  kg.  12-degree  potash  solution. 
375  kg.  potash  filler. 
750  kg.  30-degree  "  take-off  "  lye. 

In  order  to  more  surely  prevent  the  lengthening  of  the  soap  ammonia-soda  solu- 
tion also  may  be  used  in  part  in  the  filler  instead  of  potash  solution.  For  second 
and  third  quality  soap  which  can  be  filled  in  a  similar  manner  with  50  and  75  per 
cent  of  potato  flour,  the  formula  and  boiling  remain  the  same.  These  filled  "sal- 
ammoniac  turpentine"  soaps  should  be  perfumed  rather  strongly  with  sal-ammoniac 
and  some  turpentine,  for  prospective  purchasers  judge  the  soap  not  only  by  its 
white  color,  but  also  by  the  more  or  less  strong  ammoniacal  odor. 

As  already  mentioned,  the  yield  of  such  soaps  is  said  to  be  increased  by  the  use 
of  Krutolin.  This  is  explained  by  the  increased  ability  to  take  shorteners.  For 
example,  a  "sal-ammoniac  turpentine"  soap  filled  with  50  per  cent  potato  flour, 
gave  a  yield  of  about  250  per  cent. 

Krutolin  is  not  available  for  natural  grain  and  green  soft  soaps,  as  here  its  qual- 
ities do  not  make  it  a  substitute  for  either  tallow  or  linseed  oil.  Tallow  is  necessary 
for  natural  grain  soaps;  at  least  up  to  now  it  has  been  impossible  to  produce  a 
faultless  grain  formation  with  Krutolin  or  Talgol.  Krutolin  is  also  not  suited  for 
a  perfectly  clear  transparent  soft  soap. 

From  long  continued  tests  in  a  large  way  it  has  been  shown  that  Krutolin  can 
also  be  added  to  the  stock  used  in  making  bar  soaps,  insuring  light  color  with  good 
pressing  qualities. 

A  stock  giving  a  light  yellow  soap  which  presses  well,  is  the  following: 
1200  kg.  Krutolin 
1200  kg.  fatty  acids  of  Talgol 
300  kg.  fatty  acids  of  by-product  cocoanut  oil 
300  kg.  fatty  acids  of  palm  kernel  oil 
3000kg. 

450  kg.  rosin  =  15  per  cent 
3450kg. 

Under  normal  treatment  and  good  cooling  the  above  stock  will  furnish  a  soap  of 
adequate  firmness.  Of  course,  the  amount  of  rosin  added  has  an  important  influ- 
ence on  the  solidity  of  the  soap.  With  large  amounts  of  rosin  the  use  of  soft  fats 
must  be  minimized,  as  otherwise  there  is  danger  of  obtaining  too  soft  a  soap  in  spite 
of  the  cooling  treatment. 

A  stock  with  20  per  cent  rosin  has  the  following  composition: 
800  kg.  Krutolin 

600  kg.  fatty  acids  of  light  bone  fat 
1000  kg.  fatty  acids  of  Talgol 
300  kg.  fatty  acids  of  by-product  cocoanut  oil 
300  kg.  fatty  acids  of  palm  kernel  oil 
3000kg. 

J>00  kg.  rosin  =  20  per  cent 
3600  kg. 


386  THE  HYDROGENATION  OF  OILS 

To  obtain  sufficiently  solid  soaps  it  is  important  to  separate  sharply  on  salting  out 
so  as  to  secure  a  good  grain.  By  doing  this  the  appearance  of  cake  soap  may  be 
somewhat  marred.  This,  it  is  further  stated,  is  not  to  be  feared  so  much  with  cooled 
soaps,  as  undesirable  segregation  cannot  occur  to  any  material  extent  during  the 
rapid  solidification.  This  is  one  of  the  main  advantages  of  cooling  machines  in 
addition  to  the  rapid  production  of  goods  ready  for  shipment.  If  only  by-product 
cocoanut  or  palm  kernel  oil  from  edible  fat  manufacture  are  to  be  used  for  the  stock 
instead  of  the  best  palm  kernel  fatty  acid,  it  will  be  necessary  to  reduce  the  propor- 
tion of  rosin  as  the  resulting  soap  may  otherwise  be  too  soft.  These  by-product 
cocoanut  or  palm  nut  oils  almost  always  contain  sesame  or  other  similar  oils,  and 
influence  the  soap  produced  from  them.  When  Krutolin  is  used  in  this  manner  it 
is  advisable  to  perfume  with  safrol,  lemon  oil,  etc.,  before  cooling  in  order  to  cover 
the  peculiar  odor  of  this  raw  material  which  is  disagreeable  to  some  people. 

For  settled  yellow  rosin  grain  soaps  Krutolin  can  also  be  used  to  advantage  as 
it  improves  the  base  for  later  coloring.  The  action  of  crude  palm  oil  used  for  color- 
ing will  be  materially  stronger  with  a  clear  soap  base,  than  if,  for  instance,  dark 
bone  fat  has  produced  a  base  difficult  to  cover. 

The  composition  of  the  stock  is  the  following: 

600  kg.  by-product  cocoanut  oil 

900  kg.  Krutolin 

600  kg.  fatty  acids  of  light  bone  fat 

450  kg.  fatty  acids  of  Talgol 

450  kg.  crude  palm  oil 
3000kg. 

600  kg.  rosin  =  20  per  cent 
3600kg. 

Here  also  the  condition  of  the  finished  soap  must  be  the  regulator  for  its  com- 
position. For  instance,  if  the  soap  is  too  soft,  the  percentage  or  rosin  or  Krutolin 
is  to  be  reduced. 

Krutolin  also  finds  a  use  in  making  white  wax  grain  soaps  and  various  grades  c  I 
textile  soaps.  Where  the  kind  and  color  of  the  soaps  allow,  as  has  been  repeatedly 
found  with  textile  soaps,  Krutolin  should  be  split,  in  order  not  to  lose  the  glycerine. 

Krutolin  can  be  used  to  advantage  as  an  addition  fat  in  making 
soaps  by  the  cold  process,  although  care  should  be  taken  in  its  use. 
With  unfilled  toilet  soaps  about  30  per  cent  Krutolin  may  be  used 
with  about  70  per  cent  of  cocoanut  oil.  If  the  soap  is  to  be  filled, 
the  percentage  of  Krutolin  should  be  correspondingly  reduced,  since 
otherwise  the  soap  would  suffer  in  appearance  and  would  be  poorly 
bonded.* 

In  preparing  a  white  soft  soap  Bergo  (Seifen.  Ztg.  (1913),  1220)  uses  1000  kg. 
fatty  acids  of  cotton  oil  to  200  kg.  of  Candelite.  900  kg.  of  30°  Be.  caustic  potash 
lye  and  300  kg.  of  25°  Be",  caustic  soda  lye  are  used  together  with  100  kg.  of  car- 
bonate of  soda  lye  of  30°  Be.  The  caustic  potash  lye  is  reduced  with  carbonate  of 

*  Seifen.  Ztg.  (1914),  8. 


USES  OF  HYDROGENATED  OILS  387 

potash  solution.     The  lyes  are  put  in  the  kettle  first,  the  fatty  acids  slowly  added 
and  then  the  Candelite.*     (Chem.  Abs.  (1914),  588.) 

Hydrogenated  linseed  oil  has  been  put  on  the  market  under  the 
name  of  "  Linolith  "  by  the  Germania  Olwerke.f  Two  grades  are 
manufactured.  One  grade  has  a  melting  point  of  45°  C.,  and  the 
other  melts  at  55°  C.  Both  grades  show  a  saponification  number 
of  188  to  195  and  a  glycerine  content  of  9  to  10  per  cent.  Linolith 
has  not  been  used  extensively  in  white  soaps  as  it  is  off  color,  but  is 
serviceable  for  the  preparation  of  rosin  or  "Eschweger"  soaps  and  the 
like.  While  the  raw  material,  linseed  oil,  is  liable  to  cause  yellowing 
or  after-darkening  of  soaps  or  the  sweating  out  of  drops  of  a  yellow 
liquid,  the  hardened  oil  is  thought  to  be  free  from  these  objections, 
but  caution  is  advised  in  its  use  until  thorough  tests  have  been  carried 
out.t 

Soaps  made  with  hardened  linseed  oil  (Linolith)  and  rosin  are  of  good 
quality  and  the  odor  and  color  are  excellent. §  The  following  formula 
have  been  tested: 

*  The  character  of  soaps  made  from  hardened  oil  in  conjunction  with  cottonseed 
or  peanut  oil  is  discussed  in  Der  Seifenfabrikant  (1913),  31. 

f  Talgol,  Candelite,  Krutolin  and  Linolith  have  taken  a  place  in  the  German 
market  and  are  listed  among  the  fats  regularly  quoted.  (See  Seifen.  Ztg.  (1913), 
1386.) 

In  Germany  the  price  of  fish  and  whale  oils  fluctuates  to  some  extent  with  that  of 
linseed  oil  by  reason  of  the  demand  for  these  oils  by  oil-hardening  concerns.  (Seifen. 
Ztg.  (1913),  1385.) 

Linseed  oil  is  in  increased  demand  for  the  manufacture  of  hardened  oils  and  edible 
compounds.  It  is  stated  that  in  North  America  this  oil  promises  to  become  an  im- 
portant raw  material  for  the  hydrogenation  industry.  (Seifen.  Ztg.  (1913),  1277.) 

R.  H.  Adams,  president  of  the  American  Linseed  Company,  attributes  consider- 
able importance  to  the  hardening  process  as  apph'ed  to  linseed  oil.  "The  hydro- 
genation process,"  Adams  states,  "  is  merely  in  its  infancy  and  is  bound  to  exert  a 
powerful  influence  upon  the  oil  markets,  and  will  prevent  the  price  of  linseed  oil  from 
ever  going  to  the  low  levels  which  have  been  reached  in  certain  years  of  the  past." 
He  states  that  the  process  would  not  affect  linseed  oil  alone,  but  as  the  process  was 
applicable  to  other  vegetable  oils  and  to  fish  oils,  the  question  of  comparative  prices 
would  largely  determine  the  extent  of  consumption  in  the  case  of  each  oil.  The 
increased  outlet  for  linseed  oil  afforded  by  virtue  of  the  hydrogenation  process  was 
generally  credited  to  the  soap  trade.  While  consumption  of  oil  for  soap-making  pur- 
poses undoubtedly  has  increased,  Adams  states  that  another  outlet,  and  one  which 
may  assume  very  large  proportions,  is  found  in  the  edible  trades,  and  even  now  large 
quantities  of  linseed  oil  are  being  thus  consumed  on  the  Continent.  (O.  P.  &  D.  R., 
March  10,  1914.) 

J  Seifen.  Ztg.  (1913),  1299. 

§  Seifen.  Ztg.  (1914),  231. 


388 


THE  HYDROGENATION  OF  OILS 


A 

B 

C 

D 

Linolith  M   P.  45°  C.,  or  its  fatty  acids.  . 

1600  Ibs. 

1600  Ibs. 

Linolith  extra,  M.  P.  55°  C.,  or  its  fatty 
acids 

1500  Ibs 

1500  Ibs 

Fatty  acids  of  palm  kernel  oil.                .  . 

400 

200 

400 

300 

Fatty  acids  of  cocoanut  oil 

200 

Fatty  acids  of  peanut  oil  .         .       

300 

500 

500 

Fatty  acids  of  Talgol  

500 

300 

Soft  fat                              

500 

700 

300 

700 

Rosin.  . 

750 

1050 

900 

1200 

The  fatty  acids  were  saponified  with  carbonate  and  the  neutral  fat 
with  30  degree  caustic  soda.  The  Linolith  extra  was  found  capable  of 
carrying  a  higher  proportion  of  rosin  than  the  regular  Linolith. 

Linolith  does  not  exhibit  any  marked  odor  such  as  is  observed  in 
the  case  of  much  of  the  hardened  fish  oil  on  the  market  and  is  regarded 
as  suitable  for  the  manufacture  of  white  grained  soaps.*  The  follow- 
ing procedure  has  been  tried  and  a  satisfactory  product  obtained. 
50  parts  of  Linolith,  10  parts  of  a  tallowy  fat  and  40  parts  of  fatty 
acids  derived  from  a  vegetable  oil  were  employed.  The  Linolith  and 
tallowy  fat  were  saponified  and  it  was  noted  that  saponification  pro- 
gressed rapidly.  The  product  was  bleached  with  Blankit  and  salted 
out.  After  settling  it  was  combined  with  stock  derived  from  the 
separate  saponification  of  the  vegetable  oil,  and  well  boiled  and  salted 
out.  The  soap  was  duly  grained  and  afforded  a  product  of  excellent 
feel  and  good  odor.  The  color  was  not  a  pure  white. 

The  difficulties  in  using  hydrogenated  linseed  oil  (Linolith)  in  white- 
grained  soaps,  according  to  Wilhelmus,t  have  been  that  the  color  was 
not  sufficiently  light  and  the  lathering  properties  were  deficient.  The 
texture  of  the  soap  was  unsatisfactory  and  cracks  occurred  on  standing. 
In  investigations  directed  toward  the  elimination  of  these  objectionable 
features  Wilhelmus  found  that  much  depended  on  the  manner  of  cleav- 
age of  the  hardened  linseed  oil.  While  with  autoclave  treatment 
saponification  to  the  extent  of  88  to  90  per  cent  gave  fatty  acids  of  good 
color,  it  was  not  found  feasible  with  the  Twitchell  reagent  to  exceed 
80  to  82  per  cent,  as  the  resulting  fatty  acids  otherwise  were  too  dark 
for  white  soaps.  Pfeilring  reagent  afforded  better  results  and  Wilhel- 
mus regards  this  cleavage  compound  to  be  of  specific  value  in  splitting 
hardened  oils.  Benefit  is  derived  by  adding  to  hydrogenated  linseed 
oil  a  quantity  of  an  oil,  such  as  peanut  oil,  which  splits  easily,  yielding 
light  colored  fatty  acids.  By  subjecting  the  hardened  oil  to  cleavage 
under  these  conditions  a  better  grade  of  fatty  acid  may  be  obtained. 
*  Seifen.  Ztg.  (1914),  140  and  167. 
t  Seifen.  Ztg.  (1914),  257. 


USES  OF  HYDROGENATED  OILS  389 

In  making  the  soap  about  40  per  cent  of  hydrogenated  linseed  oil 
(Linolith)  may  be  employed.  After  saponification  with  alkali  and 
graining  in  the  kettle,  the  product  is  bleached.  For  this  purpose  a 
bleach  consisting  of  91  parts  of  water,  5.8  parts  of  sodium  bisulfite,  2 
parts  of  sulfuric  acid  and  1.35  parts  of  zinc  dust  are  used  for  1000  parts 
by  weight  of  the  fat.  The  use  of  soap-cooling  apparatus,  in  place  of 
frames,  enables  a  better  control  of  the  color.  The  addition  of  10  to 
15  per  cent  of  castor  oil  improves  the  solubility  and  lathering  qualities  of 
the  soap.  15  per  cent  of  castor  oil  is  the  maximum.*  If  still  higher 
lathering  properties  are  required  "Saponin"  powder  may  be  added. 

*  The  preparation  of  soaps  with  fatty  mixtures  consisting  of  saturated  fats,  such 
as  those  derived  by  hydrogenation,  with  unsaturated  fats  or  oils  has  been  made  the 
basis  of  an  application  for  German  Patent  by  Worms  and  the  novelty  of  the  idea  13 
criticized  in  Seifensieder  Zeitung,  1914,  392. 


CHAPTER  XVI 

USES    OF   HYDROGENATED    OILS    AND    PROPERTIES    OF 
CERTAIN    HARDENED    PRODUCTS 

Ittner  *  states  that  the  hydrogenation  process  has  been  worked 
out  by  a  number  of  soapmakers,  that  hydrogenated  oils  have  been 
and  are  used  on  a  comparatively  large  scale  in  soapmaking  but 
that  their  principal  employment  up  to  the  present  time  has  been  in 
the  manufacture  of  edible  fats. 

The  hydrogenation  process  has  reinstated  whale  oil  as  an  important 
fatty  commodity.  The  Oil,  Paint  and  Drug  Reporter  f  alludes  to 
the  status  of  this  oil  as  follows: 

"  About  fifty  years  ago  whale  oil  found  an  extensive  sale  for  illuminating  and 
lubricating  purposes.  So  established  became  its  use  as  a  burning  oil,  stories 
are  told  that  concern  was  sometimes  expressed  as  to  the  means  of  future  lighting 
when  the  supply  of  whale  oil  should  be  exhausted.  Stocks  of  the  oil  were  in 
the  early  days  occasionally  insufficient  for  the  demand  and  there  was  apparently 
some  color  to  these  fears.  With  the  advance  of  the  petroleum  industry  and 
the  assurance  of  relatively  low  cost  of  burning  and  lubricating  oils,  the  whaling 
industry  was  confronted  with  a  power  that  was  destined  to  undermine  its 
staunchest  support,  and  gradually  it  had  to  yield  to  the  overwhelming  economic 
force  until  about  five  years  ago  when  another  shift  in  the  fortunes  of  trade 
opened  new  and  unexpected  opportunities  for  whale  oil.  The  restoration  came 
through  the  successful  development  of  the  hydrogenation  of  oils,  which  has 
enlisted  foreign  interests  in  the  whaling  industry  on  a  large  scale,  and  the  pro- 
duction has  reached  under  modern  methods  limits  that  can  put  to  blush  the 
records  of  early  years.  According  to  the  latest  statistics,  the  world's  annual 
output  of  whale  oil  amounts  to  more  than  800,000  casks.  Instead  of  illuminat- 
ing our  darkness,  it  now  serves  mankind  liberally  as  a  soap  material,  for  which 
field  it  is  well  adapted,  while  some  measure  of  success  has  been  attained  through 
the  hydrogenation  process  for  edible  requirements.  J  In  place  of  the  old  whaling 
schooners  modern  vessels  are  now  employed  and  present  refining  methods  are  much 
more  scientific  and  capable." 

The  reduction  of  clupanodonic  acid  by  means  of  hydrogen  and  colloidal 
palladium  yields  stearic  acid  and  a  mixture  of  saturated  acids  of  low  melting- 
point.  From  this  and  other  observations  the  view  is  advanced  that  clupano- 

*  J.  Ind.  Eng.  Chem.,  1915,  936. 

fJan.  25,  1915,  9. 

J  In  view  of  the  stringency  in  Germany  of  consistent  fats,  brought  about  by  the  war, 
the  use  oi  hydrogenated  fish  oil  or  other  hardened  oil  is  advanced  as  fitting.  Chem. 
Ztg.,  1914,  1131  and  Seifen  Ztg.,  1915,  1011  and  1132. 

390 


USES  OF  HYDROGENATED  OILS  391 

donic  acid  contains  a  mixture  of  isometric  tetra  olefme  carboxylic  acids,  in  part 
having  branching  hydrocarbon  chains.* 

The  results  of  hydrogenating  torpedo  liver  oil  are  reported  by 
White.j  The  oil  was  hydrogenated  at  a  temperature  at  200°  C.,  in 
the  presence  of  reduced  nickel  supported  on  asbestos.  Hydrogen 
was  simply  bubbled  through  the  oil  which  was  placed  in  a  vessel 
heated  by  an  oil  bath.  An  oil  of  pleasant  nutty  odor  was  prepared 
by  hydrogenating  for  a  few  hours. 

According  to  TsujimotoJ  oils  from  the  livers  of  different  species 
of  Japanese  sharks  contain  a  large  proportion  of  unsaturated  hydro- 
carbons, up  to  90  per  cent  in  the  case  of  Squalus  Mitsukuri.  The 
chief  constituent  is  a  hydrocarbon,  CaoHso,  which  is  a  colorless  oil, 
with  sp.  gr.  0.8587  at  15°  C.  It  has  pronounced  drying  properties 
and  forms  a  bromine  addition  compound,  CaoHsoBm,  and  a  hydrogen 
addition  compound,  CaoH^.  The  name  "  squalene  "  is  suggested  for 
this  hydrocarbon. 

Hydrogenation  Procedure. — 3.3115  g.  of  the  hydrocarbons  of  shark-liver  oil  § 
were  dissolved  in  30  cc.  of  ether  in  a  shaking  bottle.  To  this  solution  0.5.  g. 
of  Loew's  platinum  black  was  added.  The  bottle  was  then  connected  to  a  gas 
burette,  which,  in  turn,  was  connected  with  a  hydrogen  holder.  Hydrogen 
was  prepared  from  pure  zinc  (Merck)  and  dilute  sulphuric  acid,  and  before  enter- 
ing into  the  burette,  it  was  washed  and  dried  by  bottles  containing  a  solution 
of  potassium  permanganate  and  concentrated  sulphuric  acid.  By  vigorously 
shaking  the  bottle,  hydrogen  was  conducted  into  it  under  the  mercury  pressure. 
After  two  hours  forty  minutes,  the  absorption  ended;  the  volume  of  hydrogen 
absorbed,  together  with  a  little  leakage,  was  1120  cc.  The  hydrogenated  com- 
pound, left  on  evaporating  off  ether,  was  found  to  be  a  colorless  oil,  resembling 
in  its  appearance  the  so-called  liquid  paraffin.  It  has  the  following  properties: 
Sp.  gr.  at  Y0  C.,  0.8125;  b.p.  (10  mm.  pressure)  274°  C.;  solidifying  pt.; 
at  —20°  C.  it  remained  clear  and  mobile;  80°  —  C.,  solidified  to  a  transparent 
jelly  which  at  -35°  C.  regained  its  mobility;  ref.  index  at  20°  C.,  1.4525.  It 
was  not  readily  acted  on  by  concentrated  sulphuric  acid,  even  at  100°  C. 

Elementary  Analysis.— (1)  0.1610  substance  gave  0.5022  CO.,  0.2114  H2O. 

(2)  0.1910  substance  gave  0.5059  CO2,  0.2523  H2O. 

C  =  85.07,  85.09  per  cent;    H  =  14.69  per  cent,  14.78  per  cent. 

C30H62  requires  C  =  85.21  per  cent,  H  =  14.79  per  cent. 

Molecular  weight  determination,  by  freezing-point  method,  0.2982  substance 
in  11.1030  benzol,  d=0.31°  C.  Mol.  wt.=433. 

CsoH62  requires  mol.  wt.  =422.5. 

The  substance  has,  therefore,  been  confirmed  to  be  a  compound  of  the  em- 
pirical formula  C30H62.  As  C3oH62  is  of  a  type  of  the  general  formula  CnH2n+2, 
it  appears  that  the  hydrocarbon  C3oH5o  belongs  to  the  aliphatic  compounds. 

*Seifen.  Ztg.,  1914,  1072;   Riedels  Berichte.  1914. 
t  Transactions  American  Fisheries  Society,  December  1914,  88. 
J  J.  Chem.  Ind.  Tokyo,  1916,  19,  277;  J.  S.  C.  I.,  1916,  609. 
§  Tsujimoto,  J.  Ind.  Eng.  Chem.,  1916,  889. 


392  THE  HYDROGENATION  OF  OILS 

As  to  the  uses  of  the  hydrocarbon,  Tsujimoto  states  that  only  a  brief 
investigation  has  been  made  as  yet.  It  may  be  mentioned,  however,  that  for 
technical  purposes,  the  hydrocarbon  may  be  used  for  paints,  varnishes,  lith- 
ographic inks,  and  oil  colors.  The  hydrogenated  product,  which,  in  its  appear- 
ance, is  very  similar  to  so-called  liquid  paraffins  and,  at  the  same  time,  far 
more  stable  for  cold,  will  be  a  useful  material  for  lubrication  of  machines. 

The  medicinal  use  of  the  hydrocarbon,  possible  for  the  same  purpose  as  cod- 
liver  oil,  will  perhaps  be  most  interesting,  but  careful  researches  are  necessary  to 
settle  this  question.* 

Calamary  oil  f  is  obtained  from  the  internal  organs,  especially 
the  livers,  of  various  species  of  cuttle-fish.  The  oil,  especially  the 
refined,  is  easily  hydrogenated  by  nickel  catalyzer,  giving,  according 
to  Tsujimoto,  a  white  tallow-like  fat  of  M.P.  43  to  44°  C.  and  iodine 
value  of  49.25.  Tsujimoto  believes  the  chief  use  of  the  oil  will 
probably  be  as  a  raw  material  for  hardened  oils,  as  its  price  is  below 
that  of  other  fish  oils. 

Some  details  of  the  work  of  Tsujimoto  on  clupanodonic  acid  are  of  interest 
in  view  of  the  present  extensive  application  of  the  hydrogenation  process  for 
the  deodorization  of  fish  and  whale  oils  (see  page  360).  Tsujimoto  J  has  ob- 
served a  rough  relationship  between  the  amount  of  odor  of  an  oil  and  the  degree 
of  unsaturation.  The  author  attributes  the  disagreeable  odor  of  marine  animal 
oils  largely  to  the  presence  of  glycerides  of  highly-unsaturated  fatty  acids,  espe- 
fatty  acids,  especially  those  of  the  series  C2H2n— sOz.  Thus,  Japanese  sardine 
oil,  which  contains  a  large  proportion  of  clupanodonic  acid,  has  a  much  more 
pronounced  fishy  odor  than  herring,  whale,  dab,  or  turtle  oils,  which  contain 
less  of  that  acid.  This  was  supported  by  the  fact  that  on  treating  a  solution 
of  the  fatty  acids  from  Japanese  sardine  oil  with  bromine,  filtering  off  the 
insoluble  octobromide,  and  reducing  the  brominated  fatty  acids  in  the  filtrate^ 
'{he  acids  obtained  were  practically  free  from  the  original  unpleasant  odor, 
though  still  possessing  an  odor.  The  precipitated  octobromide  was  odorless, 
but  when  reduced  with  alcoholic  hydrochloric  acid  and  zinc  dust,  it  yielded 
clupanodonic  acid  with  the  characteristic  fishy  odor  of  the  oil.  Tsujimoto, 
therefore  suggests  that  future  investigations  of  the  problem  of  deodorization  of 
these  oils  should  aim  at  either  the  complete  removal  of  glycerides  of  the  clu- 
panodonic acid  series  or  of  their  conversion  into  non-odorous  compounds. 

As  yet  no  satisfactory  method  of  extraction  of  the  clupanodonic  acid  has 
been  found,  but  the  hydrogenation  process  has  accomplished  the  alternative 
which  Tsuj  moto  advanced. 

In  a  discussion  of  the  fish-oil  industry  in  Hokkaido  (Japan), 
Ueno  §  observes  that  the  body  oils  of  herring,  sardine,  flat  fish, 
sculpin,  etc.,  which  are  obtained  in  that  locality,  are  of  inferior 
quality  and  are  used  in  the  hardened  oil  industry. 

*See  also  Chem.  Abs.,  1918,  1004. 

t  Tsujimoto,  J.  Ind.  Eng.  Chem.,  1916,  801. 

J  J.  Coll.  Eng.,  Imp.  Univ.,  Tokyo,  1908,  4,  181-191;  J.  S.  C.  I.,  1909,  316. 

§  J.  Chem.  Ind.  Japan,  1915,  798;  Chem.  Abs.,  1916,  535. 


USES  OF  HYDROGENATED  OILS  393 

Evidently,  in  the  soap  industry,  hydrogenation  has  created  very 
little  sensation  in  this  country,  Schuck  states,*  and  he  doubts  if  the 
majority  of  soap  manufacturers  have  shown  an  absorbing  interest 
in  this  question  as  they  have  not  been  forced  to  accept  hydrogena- 
tion as  a  fact  to  be  reckoned  with  in  the  manner  the  soap  manu- 
facturers on  the  other  side  of  the  ocean  have  had  to  do. 

Two  years  ago  when  hydrogenated  fats  were  put  on  the  European  market 
in  large  quantities  they  were  received  with  a  good  deal  of  skepticism,  no  doubt 
due  to  the  novelty  of  the  thing,  and  then  the  price  was  not  attractive  enough  in 
comparison  to  the  disposable  raw  materials.  Since  then,  palm-kernel  oil,  Ceylon 
cocoanut  oil,  white  greases,  etc.,  have  gone  up  in  price  to  such  an  extent  that 
the  soap  manufacturer  was  only  too  willing  to  try  his  luck  with  hydrogenated 
fats.  It  is  indeed,  an  accomplishment,  Schuck  states,  to  produce  a  very  satis- 
factory base  soap  for  toilet  soaps  from  hardened  whale  oil  when  we  consider 
that  only  a  few  years  ago  such  an  oil  would  have  been  totally  unsuitable  for 
either  toilet  or  laundry  soaps.  It  is  quite  evident  that  a  white  soap,  for  in- 
stance, made  from  hardened  whale  oil  alone  would  be  just  as  unsuitable  for 
the  trade  as  one  made  from  a  high-titre  tallow.  The  soap  would  hardly  lather, 
would  be  too  brittle  and  would  crack.  Mistakes  were  made  at  first  by  taking 
too  high  a  percentage  of  hardened  fat  until  experience  taught  a  successful  blend- 
ing of  30  to  50  per  cent  of  the  latter  with  70  to  50  per  cent  of  a  softer-bodied 
fat  or  oil.  A  fat  composition  of  50  per  cent  of  the  hardened  oil,  20  per  cent 
palm-kernel  oil  or  cocoanut  oil  and  30  per  cent  peanut  oil  has  proved  to  be 
a  splendid  formula  for  white  soaps.  The  very  fact  that  this  hardened  whale 
oil  had  to  be  blended  with  soft-bodied  oils  and  fats  in  order  to  produce  a  soap 
easily  soluble  in  water  made  the  manufacture  of  rosin  soaps  that  much  easier. 
In  European  countries  soapmakers  do  not  use  such  high  percentages  of  rosin  in 
their  laundry  soaps  as  we  do  here,  and  a  percentage  of  40  per  cent  rosin  is 
considered  there  extremely  high. 

Below  is  a  formula  of  a  rosin  soap,  typical  of  the  German  pale  yellow  soaps: 

1500  Ib.  hardened  linseed  oil  (linolith)  fatty  acids. 
500  Ib.  peanut  oil 
700  Ib.  soft-bodied  grease 
300  Ib.  palm-kernel  oil 

3000  Ib 

1200  Ib.  rosin =40  per  cent 

4200  Ib. 

Prior  to  the  advent  of  the  hydrogenation  process,  Schuck  observes,  linseed 
oil  was  used  almost  entirely  for  soft  potash  soaps  and  whoever  tried  to  use  it 
in  laundry  soaps,  even  in  very  limited  quantities,  was  sadly  disappointed.  The 
trouble  resided  not  alone  in  its  soft-bodied  character,  but  in  the  fact  that  the 
unsaturated  linolic  and  linolenic  acids  produced  in  a  short  time  yellow  and 
brown  spots  on  the  surface  of  the  soap  and  made  it  quite  unsalable.  Here  also, 

*  Soap  Gazette  and  Perfumer,  1914,  419. 


394  THE  HYDROGENATION  OF  OILS 

says  Schuck,  hydrogenation  has  done  wonders.  It  changed  the  physical  char- 
acter of  the  oil  entirely.  Consider,  on  the  one  hand,  the  fast  drying,  soft- 
bodied,  yellow  and  fishy-smelling  linseed  oil  and,  on  the  other  hand,  the  hard- 
ened product,  white,  hard,  non-smelling  and  suitable  for  any  kind  of  soap,  be  it 
laundry  or  toilet  soap.  Experience  has  proven  that  even  on  long  aging  the 
characteristic  yellow  and  brown  spots  of  the  linolic  and  linolenic  acids  do  not 
appear  on  soaps  made  from  hardened  linseed  oil. 

Soaps  made  from  hardened  linseed  oil  showed  at  first  a  slight  reddish  discolora- 
tion, but  this  was  rather  the  fault  of  inexperienced  settling  of  the  soap  than  of 
the  fat  itself.  The  brittleness  of  the  soap  which  the  first  batches  showed  was 
subsequently  overcome  by  a  proportionate  blending  of  linolith  with  peanut  oil  or 
castor  oil.  Castor  oil  soaps  have  the  peculiar  faculty  of  remaining  liquid  even  if 
highly  concentrated  and  for  that  reason  are  splendid  supplementary  soaps  to 
those  made  from  hardened  fats.  The  percentage  of  castor  oil  need  not  exceed 
15  per  cent  to  result  in  a  soap  which  is  easily  soluble  in  water  and  which  pos- 
sesses very  good  lathering  qualities.  Schuck  concludes  with  the  suggestion  of  a 
prophecy  that  the  time  may  not  be  so  far  off  when  hydrogenated  raw  materials 
will  be  as  universally  used  in  this  country  as  abroad  and  that  fore-knowledge 
is  very  often  half  of  the  battle.. 

At  one  time,  Knorre  *  observes,  it  was  thought  that  hardened  oils 
would  displace  all  other  fats  in  the  soap  industry  but  the  difficulties 
encountered  with  hydrogenated  fish  and  whale  oil  in  soap  making 
changed  this  view. 

Soaps  made  from  the  latter  fats  were  "  stone-hard,"  very  brittle,  were  pressed 
with  difficulty  and  lathered  poorly.  The  odor  of  the  soap  was  unpleasant, 
especially  after  keeping  for  a  considerable  time,  the  initial  white  color  changed 
to  yellow,  yellowish  red  or  brown  and  on  the  surface  of  the  cakes  varnish-like 
exudations  of  strong  odor  appeared.  Samples  of  grained  soap  of  a  neutral  char- 
acter, firm  consistence  and  good  tallowy  odor,  prepared  from  hardened  train  oil 
on  keeping  for  a  few  weeks  in  a  closed  box,  changed  materially  in  this  time. 
The  cakes  were  fissured,  the  color  was  a  rusty  brown  and  the  odor  was  disa- 
greeable. For  these  reasons  hardened  fish  and  whale  oil  can  be  recommended 
for  use  in  soaps  only  in  moderate  amounts.  The  allegation  that  these  hardened 
fats  serve  as  substitutes  for  palm  kernel  and  cocoanut  oil  is  without  support. 

Fatty  acids  can  be  obtained  from  hardened  fats  by  autoclave,  Twitchell  or 
ferment  cleavage.  In  the  autoclave  process,  zinc  powder  is  the  best  cleavage 
agent  because  the  resulting  fatty  acids  are  the  least  discolored.  When  decom- 
posing the  products  of  the  autoclave  treatment  with  sulphuric  acid,  agitation 
is  secured  by  means  of  a  current  of  air.  The  glycerine  obtained  is  of  good  qual- 
ity and  contains  0.2  to  0.5  per  cent  ash.  It  may  be  rendered  entirely  white  by 
treatment  with  blood  charcoal  in  vacuum. 

In  the  table  below,  the  properties  of  the  fatty  acids  obtained  from  several 
grades  of  hardened  fish  and  whale  oil  are  given  by  Knorre;  the  names  by  which 
these  products  are  sold  in  the  German  market  being  used. 

The  direct  pressing  of  the  fatty  acids  of  Candelite  is  not  recommended.  It 
is  better  to  mix  Candelite  and  tallow  or  refined  bone  fat,  subject  to  cleavage 

*  Self  en.  Ztg.,  1914,  806. 


USES  OF  HYDROGENATED  OILS 


395 


•O.-^-Hl 

§  *g  3  3?  35  g 

•jaqum^  auipoj 

O    rH   (N   CO  CO   O5 

"juao  aa<j 
'^Bjj  iBJ^na^ 

00   •—  <.  O   O5   OO   Tt* 

^    ^    O    O    i-*    i-H 

iC1   O^    O^   O^   CO   CO 

•jaquinjsj 
uoiiBoijiuodBg 

O    00    i-H    O5    i-H     i-t 

•jaquinjs^  ptay 

CO   r-<   1-1   CO   O   O 
t>.   CO   t~   Oi   T-H    CO 

oo  oo  oo  oo  os  a> 

•^iiiqByiuodBg 

CO    Tt<    O5    CO    "-(    Tf 
CO    1C    (N    ^H    CO    -^ 

'[BUa^BJ^ 
A^BJ-UO^ 

Tt<    CO    i—  1    t>-    O5    CO 
CO   <*   l^   00   CO    »0 

O   O   O   O   O   CD 

•ajqegmodBsuQ 

C<l     l—  1     O5     i-H     CO     i-H 

i-t    CO    Tj<    IO    <N    CO 
O   O   O   O   O   O 

•qsy 

i-l         •    rH    IO    00    O 

O       •   O   O   O   1-1 
O       •   O  O   O   O 

•3ai^jQ  ao  ssoq 

?5    i-H    W    CO    CO    i-( 
O   O   O   O   &   O 

1 

Tallowy  hard  mass.  Snow  white 
Odor,  sweet.  Hard 
Crystalline.  Snow  white 
Very  hard.  Tallowy 
Tallowy 
Hard  crystalline  mass 

II!!!03 

i 

Talgol  fatty  acids  
Olinit  fatty  acids  
Talgit  fatty  acids  
Talgol-extra  fatty  acids  . 
Candelite  fatty  acids.  .  . 
Candelite-extra  fatty  aci 

396  THE  HYDROGENATION  OF  OILS 

and  then  mix  the  fatty  acids  with  olein  or  runnings  from  hot  pressing  in  order 
to  improve  the  pressing  operation.* 

As  already  mentioned,  hydrogenafced  oils  have  been  receiving  con- 
siderable criticism  by  the  soap  makers  because  of  the  relatively  low 
lathering  qualities  of  soaps  prepared  from  these  oils. 

The  addition  of  a  large  proportion  of  hydrogenated  oil  to  the  soap  batch  is, 
therefore,  precluded.  In  order  to  secure  a  free  lathering  soap  from  hydrogenated 
fatty  material,  the  author  f  first  polymerizes  the  oil  and  then  subjects  it  to 
the  hydrogenation  process.  The  polymerization  is  carried  out  by  protracted 
heating  preferably  in  the  absence  of  air  until  the  iodine  number  has  been  re- 
duced to  as  low  a  degree  as  is  feasible.  This  reduction  depends  upon  the  oil 
which  is  being  treated.  Fish  or  whale  oil  may  have  the  iodine  number  readily 
reduced  by  polymerization  to  about  80  or  90.  Such  products  usually  still  possess 
a  fishy  odor  and  by  hydrogenating  to  an  iodine  number  of  40  or  50  the  odor  is 
eliminated  and,  in  some  cases,  the  taste  becomes  fairly  bland.  The  author  has 
prepared  soaps  from  such  products  and  finds  them  to  possess  relatively  good  lath- 
ering properties  and  to  yield  soaps  in  other  respects  of  quite  satisfactory  quality. 

Further  details  of  the  joint  result  of  polymerizing  and  hydrogen- 
ating a  fatty  oil  are  described  below.  | 

Fatty  acids  and  unsaturated  oils  such  as  the  glycerides  containing  more 
especially  two  or  more  double  bondings  or  olefine  groupings  are  capable  of  poly- 
merization at  elevated  temperatures  resulting  in  a  thickening  of  the  oil  due  not 
so  much  to  the  formation  of  stearine  as  to  the  formation  of  oil  complexes  by 
the  union  of  oil  molecules  one  with  another,  usually  denoted  by  a  profound 
reduction  of  the  iodine  number  and  other  changes.  In  this  manner  castor,  fish, 
whale,  cotton,  corn,  linseed,  rape  and  tung  oil  and  the  like  may  be  polymerized 
to  differing  degrees  and  by  such  polymerization  a  thickening  of  the  oil  usually 
occurs  which  produces  a  body  of  viscosity  that  enables  one  to  obtain  by  hydro- 
genation, a  product  containing  a  fatty  derivative  of  good  texture  or  consistency. 
The  product  may  be  used  in  making  lubricants,  or  may  be  sulfonated  by  treat- 
ment with  sulphuric  acid  or  soaps  may  be  prepared  by  saponification  with 
alkalies. 

When  catalyzers  such  as  nickel  oxide  are  employed,  it  is  preferred  first  to 
polymerize  the  oil  at  about  250°  C.  and  then  to  reduce  the  temperature  and 
harden  by  means  of  hydrogen  or  hydrogen  and  oxygen  at  a  temperature  around 
200°  C.  When  using  palladium  the  temperature  may  be  much  lower. 

Hardened  or  hydrogenated  oil  produced  by  simple  hydrogenation  is  not 
capable  of  yielding  soaps  having  as  free  lathering  qualities  as  often  as  desired, 
while  some  grades  of  the  polymerized  and  hardened  hydrogenated  oil  show  supe- 
rior lathering  qualities  when  converted  into  soap. 

To  remove  the  odor  from  fish  and  whale  oil  by  hydrogenation  requires  a  con- 
siderable conversion  to  stearine.  Usually  it  is  necessary  to  reduce  the  iodine 
number  of  fish  oil  to  40  or  50  in  order  to  convert  the  unsaturated  bodies  such 
as  clupanodonin  which  are  supposed  to  be  more  or  less  odor-producing  into  more 

*  Seifen.  Ztg.,  1914,  812. 

t  U.  S.  Patent  No.  1,151,002,  August  24,  1915. 

J  U.  S.  Patent  No.  1,178,142,  April  4,  1916. 


USES  OF  HYDROGENATED  OILS  397 

saturated  or  entirely  saturated  bodies  rendering  the  oil  free  from  disagreeably 
fishy  odor.  But  hydrogenation  to  this  point  produces  so  large  a  proportion  of 
stearine  which  lathers  freely  as  a  soap  only  in  very  hot  or  boiling  water  that  the 
product  when  used  with  cold  or  slightly  warm  water  is  deficient  in  lathering  and 
consequent  detergent  properties.  By  polymerization  the  property  of  cold  lath- 
ering existent  in  the  soaps  produced  from  normal  fish  oil  is  to  a  considerable 
degree  present  in  the  polymerized  oils  and  any  further  hardening  which  may  be 
desired  and  which  is  secured  by  hydrogenation  does  not  impair  these  lathering 
qualities  to  any  material  degree  in  connection  with  the  production  of  fats  for 
making  hard  soaps.  Hence,  polymerization  enables  the  production  from  oils 
and  fats  of  a  thickened  or  hardened  product  without  the  necessity  of  carrying 
hydrogenation  forward  to  such  a  degree  that  the  lathering  properties  of  the 
soap  are  seriously  impaired. 

The  following  procedure  will  serve  to  illustrate  the  foregoing:  Whale  oil 
was  heated  in  an  atmosphere  of  carbon  dioxide  for  sixteen  hours  at  a  tem- 
perature between  250°  and  270°  C.  The  final  product  was  viscous  and  the 
fishy  odor  was  largely  eliminated.  The  iodine  number  of  the  oil  before  heating 
was  135.5  and  that  obtained  after  heating  had  an  iodine  number  of  89.7.  The 
polymerized  oil  was  treated  with  hydrogen  in  the  presence  of  nickel  material 
as  a  catalyzer  and  a  product  was  obtained  which  did  not  appear  to  have  any 
very  definite  melting-point.  Changes  in  temperature  between  quite  wide  ranges 
did  not  appear  to  affect  the  consistency  very  materially.  It  melted  completely  at 
about  37°  C.  and  the  iodine  number  was  found  to  be  65.9.  A  quantity  of  the 
whale  oil  which  had  not  been  polymerized  was  hydrogenated  under  the  same 
conditions  and  soaps  prepared  from  both  the  products  by  saponification  with 
alkali  under  like  conditions.  The  soap  obtained  from  the  hydrogenated  whale 
oil  had  almost  no  lather  in  cold  water,  while  the  polymerized  and  hydrogenated 
product  gave  a  copious  lather  in  water  of  the  same  temperature.  The  fats  as 
well  as  the  corresponding  soaps  were  free  from  any  fishy  odor.  It  appears  to 
be  an  approximately  correct  statement  that  the  lathering  qualities  of  a  soap 
depend  on  the  melting-point  of  the  fats  from  which  it  is  made.  A  soap  made 
from  oleic  acid  lathers  rather  easily  in  cold  or  slightly  warm  water,  while  that 
made  from  stearic  acid  requires  a  temperature  of  nearly  80°  C.  to  develop  a 
satisfactory  lather.  The  absence  of  any  definite  melting-point  in  the  partic- 
ular product  illustratively  given  herein  possessed  no  very  definite  melting-point, 
as  stated  and  was  capable  of  lathering  freely  in  cold  or  tepid  water.  Soaps 
prepared  from  oils  which  are  highly  unsaturated  such  as  linseed  oil  or  fish  and 
whale  oils  are  often  prone  to  discolor  due  to  the  tendency  to  oxidation  of  some 
of  the  unsaturated  constituents.  If  the  oil  is  hardened  to  a  point  where  dis- 
coloration is  not  liable  to  take  place  and  undesirable  odors  are  removed  the 
lathering  qualities  are  impaired,  while  by  polymerizing  a  goodly  proportion  of 
the  components  which  tend  to  bring  about  oxidation  are  eliminated  without  any 
material  detrimental  influence  on  the  lathering  properties  and  by  final  treat- 
ment with  hydrogen  a  sufficient  amount  of  consistent  material  is  obtained  to 
give  the  requisite  body  or  firmness  to  the  soap.  The  amount  of  hydrogen  re- 
quired is  less,  which  is  a  saving  in  cost. 

Polymerization  of  unsaturated  oils  by  the  action  of  ultraviolet  light 
in  the  presence  of  reducing  gases  is  noted  by  Ellis.* 

*U.  S.  Patent  No.  1,180,025,  Apr.  18,  1916,  and  1,179,414,  Apr.  18,  1916. 


398  THE  HYDROGENATION  OF  OILS 

The  hydrogenation  process  enables  olein  (oleic  acid)  to  be  pre- 
pared in  two  ways  according  to  Dubovitz  *  either  by  treating  hydro- 
genated  fatty  acids  of  a  titre  of  40  to  46  in  the  usual  way  to  sep- 
arate stearine  and  olein  or  to  hydrogenate  cheap  oil  of  high  iodine 
number  to  bring  the  iodine  number  to  about  80  or  90  or  approxi- 
mately that  of  olein,  and  saponify  this  product.  The  resulting  olein 
contains  only  a  few  tenths  of  a  per  cent  of  unsaponifiable  matter 
and  a  few  per  cent  of  neutral  fat.  The  liquid  fatty  acid  contains 
highly  unsaturated  components  in  spite  of  the  iodine  number  of 
80  to  90. 

The  application  of  hardened  oils  in  the  candle  industry  is  noted 
by  Bontoux  f  who  states  that  the  operations  of  pressing  or  distilla- 
tion, impose  a  limit  on  the  degree  of  hardening  practicable. 

In  splitting  fats  with  aromatic  sulpho-fatty  acids,  the  color  of  the 
resulting  product  is  improved  by  using  hydrogenated  castor  oil,  contain- 
ing hydroxyl,  for  preparing  the  dissociating  agent.  One  part  each  of 
hardened  castor  oil  and  naphthalene  are  ground  to  a  powder  and  treated 
with  four  parts  of  commercial  sulphuric  acid  at  a  temperature  below 
20°  C.  The  resulting  product  is  poured  into  eight  parts  of  water  and 
the  upper  layer  which  forms  is  collected  and  used  as  a  fat  splitting 
agent.  { 

Formulas  for  the  production  of  white-grained  soap  employing  hardened 
linseed  and  fish  or  whale  oils  are  given  in  Seifensieder  Zeitung,  1914,  644,  705 
and  931.  A  soap  or  soap  powder  of  great  detergent  power  is  described  in  the 
same  journal,  p.  511. 

A  grade  of  hardened  linseed  oil  (linolith)  made  for  the  German  market  pro- 
duces a  toilet  soap  base  of  pure  white  color  §  see  also  Seifensieder  Zeitung, 
1914,  540,  for  approved  formulas  by  Schaal  employing  hardened  fish  oil.  On 
page  543  Bergo  gives  a  number  of  soap  stock  formulas  using  Linolith,  Talgol  or 
Candelite. 

Timely  substitutes  for  cocoanut  oil  soaps  are  discussed  by  Schaal.  ||  At 
least  40  to  50  per  cent  of  cocoanut  oil  must  be  used  to  secure  easy  saponifica- 
tion,  rapid  lathering  and  general  appearance.  Four  formulas  are  given  using 
tallow,  hardened  oil,  hog  fat  and  castor  oil  in  varied  proportions.il 

In  Germany,  during  the  war,  hydrogenated  fats  have  played  an  important 
part  in  soap  making.  The  lack  of  lathering  power  in  soaps  made  from  hard- 
ened oil  can  be  corrected,  according  to  Davidsohn  **  by  additions  of  cocoanut 

*  Seifen.  Fabrikant,  1915,  137  and  157,  Seifen.  Ztg.,  1915,  459. 
t  Matures  Grasses,  1914,  4194;   Seifen.  Ztg.,  1914,  987. 

J  German  Patent  298,773,  Vereinigte  Chem.  Werke,  A.  G. ;  American  Perfumer, 
1918,  382. 

§  Schaal,  Seifen.  Ztg.,  1914,  600. 
||  Seifenfabr.,  1914,  1158. 
1  Chem.  Abs.,  1915,  389. 
**  Chem.  Ztg.,  1915,  330. 


USES  OF  HYDROGENATED  OILS  399 

or  palm-kernel  oil,  or  rosin.  A  soap  prepared  from  50  parts  hardened  linseed 
oil,  30  parts  cocoanut-oil  fatty  acids  and  20  parts  of  rosin  exhibited  good  lath- 
ering properties.  A  cold  process  soap  made  from  40  parts  hardened  oil  and  60 
parts  cocoanut  oil  possessed  an  excellent  appearance  and  the  lathering  powers 
were  good. 

The  advantageous  utilization  of  hardened  fats  in  soap-making,  specially 
during  the  war,  is  discussed  in  Seifensieder  Zeitung,  1914,  1109.  Various  for- 
mulas are  given.  For  methods  of  making  soft  soaps  from  these  materials,  espe- 
cially Talgol  and  Krutolin,  see  Seifensieder  Zeitung,  1914,  1130. 

The  commercial  application  of  the  hydrogenation  process  to  the  French  soap- 
making  industry  is  described  by  Gurney.* 

In  connection  with  considerations  involved  by  the  war,  it  has  been  pointed 
out  f  that  the  Oelwerke  Germania  is  owned  by  the  firm  of  Jurgens,  which  is 
operated  by  Holland  and  British  capital.  A  response  to  this  comment  appears 
in  Seifensieder  Zeitung,  1914,  1073. 

At  an  exposition  in  Magdeburg  J  the  Oelwerke  Germania  of  Emmerich 
exhibited  a  series  of  hardened  oils,  viz.;  Durotol  M.P.  60°,  Coryphol  M.P. 
80°  C.,  Talgol,  Talgol  extra,  Linolith,  stearine  and  olein  from  Talgol  extra,  crude 
glycerine  from  linolith,  stearine  candles  from  Talgol  extra  and  various  soaps 
made  from  hardened  fats.  One  of  these  was  a  toilet  soap  containing  43  per 
cent  of  hardened  linseed  oil.  (Linolith.) 

The  Oil,  Paint  and  Drug  Reporter  §  reviews  the  progress  of  hydro- 
genation during  1913  and  notes  that  because  of  the  relatively  low 
price  of  linseed  oil  in  Europe  this  oil  has  been  more  generally  hard- 
ened for  soap  makers  than  other  oils.  Abroad,  cottonseed  oil  is  not 
hardened  extensively,  except  for  edible  purposes.  Small  quantities 
are  being  hardened  for  margarine,  and  this  will  probably  be  an 
important  business.  The  total  capacity  of  the  European  hardening 
plants  for  1914  is  put  at  1,375,000  barrels  (400  Ib.  each),  but  not 
more  than  half  this  amount  was  made  in  1913.  In  the  U.  S.  the 
output  for  1913  is  put  at  500,000  barrels  and  is  rapidly  increasing. 

During  1917  an  extraordinary  demand  from  soap  and  candle  makers  kept  the 
white  and  yellow  grease  stearine  market  at  Chicago  strong  throughout  the  year.|| 
Although  the  record-breaking  prices  which  prevailed  during  the  year  was  a  stimulant 
to  production,  supplies  of  stearines  were  never  burdensome  during  1917.  Early 
in  the  year  oleo  stearine  attracted  a  good  premium  over  tallow  due  to  the  strong 
demand  from  compound  makers,  but  later  in  the  year  the  demand  from  this  source 
waned  somewhat  when  the  hydrogenation  of  bean  oils  for  oleo  stearine  was  carried 
out  extensively.  The  substitution  of  the  hydrogenated  bean  oils  for  oleo  stearine 
reduced  the  demand  for  stearine  on  the  part  of  compound  makers  to  a  minimum. 

*  Chem.  Trade  J.,  55,  187. 
t  Seifen.  Ztg.,  1914,  1030. 
J  Seifen.  Ztg.,  1914,  863. 
§  July  20,  1914;  J.  S.  C.  I.,  1914,  837. 
||  O.  P.  &  D.  Reporter,  1918,  71. 


400  THE  HYDROGENATION  OF  OILS 

Hydrogenated  cocoanut  oil  obtained  from  Oelwcrke  Germania  of 
Emmerich,  was  used  by  Schrauth  *  in  preparing  certain  special  soaps; 
one  grade  of  which  contained  oxycyanide  of  mercury.  The  lack  of 
lathering  properties  of  hardened  oil  soap  is  overcome  by  the  addi- 
tion of  castor  oil  or  turkey-red  oil  (5  to  10  per  cent).| 

The  cost  of  hydrogenating  fatty  oils  according  to  Bontoux  J  at 
first  was  figured  at  7  to  8  francs  per  hundred  kilos  of  oil  but  at  the 
present  time  certain  patent  owners  are  guaranteeing  a  maximum 
cost  of  3  to  4  francs  per  hundred  kilos,  depending  on  the  nature  of 
the  oil  and  its  intended  use. 

Schrapinger  §  has  studied  the  hydrogenation  of  Chinese  wood  oil 
in  order  to  throw  some  light  on  the  structure  of  wood  oil  fatty  acid. 
Reduction  could  not  be  carried  out  by  the  method  of  Erdmann  and 
Bedford  1 1  because  the  acid  polymerizes  under  the  conditions  imposed. 

Accordingly  Schrapinger  used  the  method  of  Paal  H  (palladium-hydrosol  as 
hydrogen  carrier),  and  the  modification  by  A.  Skita  (higher  pressure,  for  the 
purpose  of  accelerating  the  reaction). 

The  wood-oil  acid  to  be  reduced  was  dissolved  in  30  cc.  of  alcohol.  The 
palladium  chloride  was  dissolved  in  50  cc.  of  boiling  water;  0.5  g.  of  gum  arabic 
was  also  separately  dissolved  in  50  cc.  of  water.  The  two  solutions  were  mixed 
after  cooling,  and  the  alcoholic  wood-oil  acid  solution  was  added;  enough  ether 
and  alcohol  was  then  added  so  that  a  uniform  liquid  was  obtained.  Hydrogen, 
under  one  atmosphere  pressure,  was  then  forced  into  this  mixture,  and  the 
closed  vessel  shaken  during  the  process.  In  two  separate  experiments,  the  sodium 
salt,  as  well  as  the  free  acid,  was  reduced.  It  was  found  that  the  sodium  salt 
reduces  better  than  the  acid  itself,  owing  to  the  greater  solubility  of  the  sodium 
salt  in  aqueous  alcohol,  thus  eliminating  the  possibility  of  coating  the  colloidal 
palladium  particles  by  precipitated  acid. 

After  the  reaction  was  finished,  the  solution  was  raised  to  boiling,  then  fil- 
tered and  finally  evaporated.  The  residue  was  dissolved  in  hot  water,  and 
acidulated  with  hydrochloric  acid.  The  precipitated  acid  was  recrystallized 
from  alcohol,  possessed  a  melting-point  of  69°  to  69.5°  C.  and  showed  the  fol- 
lowing composition: 

1.  0.2138  g.  substance  gave: 

0.5969  g.  CO2  corresponding  to  0.1627  g.  C., 
0.2386  g.  H2O  corresponding  to  0.0266  g.  H. 

2.  0.1941  g.  substance  gave: 

0.5424  g.  CO2  corresponding  to  0.1479  g.  C., 
0.2135  g.  H2O  corresponding  to  0.0238  g.  H. 

*  Seifen.  Ztg.,  1915,  17,  371;   Soap  Gazette  and  Perfumer,  1915,  424. 
t  Seifen.  Ztg.,  1914,  992. 

J  Matieres  Grasses,  1914,  4194;   Seifen.  Ztg.,  1914,  987. 

§  Dissertation,  Karlsruhe,  1912;  Stevens  and  Armitage,  China  Wood  Oil,  Vol.  II, 
Part  2,  2770. 

||Ber.  1909,  42,  1324. 

1  Ber.,  1905,  38,  1406,  2414;    1907,  40,  2209;    1908,  4.1,  2273,  2282. 


USES  OF  HYDROGENATED  OILS  401 

Calculated  for  Ci8H36O2  C  =  75.98  per  cent,  H  =  12.76  per  cent, 

Found  C  =  76.09  per  cent,  H  =  12.44  per  cent, 

C  =  76.19  per  cent,  H  =  12.26  per  cent 

The  product  obtained,  therefore,  was  stearic  acid,  whereby  it  was  proven  that 
elaeomargaric  acid  is  an  acid  with  a  simple  (straight)  chain.  Yield:  63  per  cent 
of  the  theory. 

A  procedure  given  by  Levinstein  *  relates  to  the  production  of 
compounds  from  hydrogenated  saponifiable  fats  or  oils  and  to  the 
production  therewith  of  compositions  from  waxes,  fats,  oils,  or  the 
like,  which  are  soluble,  miscible,  or  emulsifiable  in  water  without  the 
addition  of  alkali. 

The  compositions  obtained  are  stated  to  be  valuable  in  the  preparation  and 
treatment  of  leather,  and  in  the  textile  industries,  as  special  finishes. 

In  carrying  this  method  into  effect,  hardened  oils  obtained  by  the  hydrogena- 
tion  of  saponifiable  fats  or  oils,  such,  for  example,  as  hardened  fish  oil  or  hard- 
ened linseed  oil,  are  treated  under  certain  conditions  with  sulphuric  acid.  The 
sulpho  compounds  so  obtained  have  the  property  of  making  mineral  and  other 
waxes,  oils,  fats,  or  the  like  soluble,  miscible  or  emulsifiable  in  water. 

In  order  to  obtain  these  sulpho  compounds,  hardened  linseed  oil,  for  example, 
is  selected,  and  after  melting  is  treated  with  sulphuric  acid  until  a  sample 
from  the  mass  gives  an  emulsion  with  water,  or  until  a  washed  sample  practi- 
cally dissolves  in  ammoniacal  water.  The  mass  is  then  poured  into  water  pre- 
viously heated  to  30°  C.,  when  the  sulpho  compound  will  separate  in  the  form 
of  a  white  pulpy  mass. 

The  following  is  an  example  of  how  a  sulpho  compound  may  be  produced 
and  how  such  compound  may  be  used  to  produce  a  soluble  composition  with 
mineral  wax: 

One  hundred  parts  of  hardened  linseed  oil  are  melted  and  then  cooled  to 
about  35°  C.  under  agitation.  Twenty-five  parts  sulphuric  acid  (100  per  cent 
H2SO4  monohydrate)  are  then  added  gradually  and  the  temperature  is  kept 
between  40°  to  45°  C.  until  a  washed  sample  is  practically  soluble  in  hot  water. 
The  whole  is  then  run  into  a  salt  solution  (10°  Tw.)  which  has  been  heated  to  a 
temperature  of  30°  C.,  is  well  stirred,  and  then  allowed  to  settle,  after  which  the 
salt  water  is  drawn  off.  The  washing  with  salt  water  is  again  repeated  until 
the  mineral  acid  has  been  removed,  or  the  mineral  acid  may  be  neutralized 
with  alkali.  The  sulpho  acid  of  hardened  linseed  oil,  thus  obtained,  when 
melted  and  mixed  with  equal  parts  of  paraffin  wax  gives  a  composition  which 
is  practically  soluble  in  hot  water  without  the  addition  of  alkali. 

The  hardened  oils  can  be  sulphonated  when  mixed  with  oils  or  greases,  but 
the  property  possessed  by  the  product  of  making  waxes  miscible  or  soluble  or 
emulsifiable  in  water  without  neutralizing  the  sulpho  acid  or  without  any  addi- 
ton  of  alkali,  appears  to  be  to  some  extent  diminished.! 

Experiments  on  the  catalytic  hydrogenation  of  two  kinds  of  oil 
from  the  French  colonies,  namely,  "  Karite  "  of  French  West  Africa  and 

*  U.  S.  Patent  No.  1,185,414,  May  30,  1916. 

t  British  Patent  No.  16,890,  July  16,  1914;  J.  S.  C.  I.,  1915,  913;  Chem.  Abs.,  1916, 

288. 


402 


THE  HYDROGENATION  OF  OILS 


"  Aouara  "  of  Guiana  have  been  carried  out  by  Heim  and  Hebert.* 
Karite  (Butyrospermum  parkii)  butter  and  fat  of  Aouara  nuts 
mixed  with  catalyzer  were  placed  in  flasks  and  pure  dry  hydrogen 
was  passed  through  at  a  pressure  of  1  to  2  cm.  of  mercury  above 
atmospheric  pressure.  The  process  was  carried  out  at  50°  and  also 
at  180°  to  200°  for  twelve  hours  with  constant  agitation.  As  cata- 
lyzers reduced  platinum  in  the  proportion  of  1  per  cent  and  reduced 
nickel,  5  per  cent,  were  used.  At  the  end  of  the  process  the  mix- 
ture was  dissolved  in  benzine  and  the  fat  obtained  by  evaporation. 
Results  are  given  in  the  following  table  :f 


KARITE  BUTTER. 

FAT  OF  AOUARA  NUTS. 

Treatment. 

Melting- 

Iodine 

Melting- 

Iodine 

point. 

Value. 

point. 

Value. 

Initial 

32° 

65  6 

30° 

9  5 

After  hydrogenation  with  Pt.  at  50°  

35° 

57.6 

30°-31° 

9.2 

After  hydrogenation  with  Pt.  at  180°-200°. 

67°-68° 

16.0 

32° 

8.1 

After  hydrogenation  with  Ni  at  50°  

34°-35° 

48.0 

30°-31° 

9.0 

After  hydrogenation  with  Ni  at  180°-200°. 

69°-70° 

9.6 

32° 

6.7 

Padoa  and  Dalla  J  describe  a  process  of  deodorizing  and  decolor- 
izing chrysalis  oil  by  passing  a  current  of  air  or  hydrogen  or  a  mix- 
ture of  these  gases,  at  140°  to  250°,  through  the  oil,  to  which  may  be 
added  a  catalyzer.  The  decolorization  of  the  oil,  which  becomes 
brown  as  a  result  of  the  treatment,  is  effected  by  shaking  with 
dichromate  and  H^SCX.  The  oxides  of  nickel,  cobalt,  iron,  manga- 
nese, copper,  lead,  cerium,  etc.,  are  specified  as  suitable  catalyzers. § 

Schmitz  i|  reports  that  the  hydrogenation  of  crude  naphthenic 
acids,  employing  a  catalytic  agent,  did  not  affect  the  odor  or  prop- 
erties of  these  acids. 


LUBRICANTS  CONTAINING  HARDENED  OIL 

F   Krist  H  has  supplied  the  following  formulas  which  he  states  were  furnished  by 
Georg  Schicht  A.-G.,  Aussig. 

*  Miniature  des  Colonies,  Bull,  de  1'Office  Colonial  50,8,  238-44,   1915;    Bull.  Agr. 
Intelligence  6,  1247-8,  1915. 
fChem.  Abs.,  1916,  1106. 

J  Italian  Patent  No.  138,942,  May  5,  1914;   Chem.  Abs.,  1915,  2822. 
§See  also  Tsujimoto,  Chem.  Ztg.,  1914,  110. 
||  Mat.  grasses,  7,  4115;  J.  S.  C.  I.,  33,  684. 
1  Seifen.  Ztg.,  1913,  776. 


USES  OF  HYDROGENATED  OILS  403 

1.  Very  consistent  and  uncolored  compound  for  heaviest  types  of  machinery. 

40    Kilos  hardened  oil  (Talgit); 

3.5  Kilos  caustic  potash  solution  50°  Be; 

13    Kilos  caustic  soda  solution  37°  Be; 

75     Kilos  American  mineral  oil  sp.  gr.  0.870. 

2.  Colored  compound  for  heavy  machinery. 

40  Kilos  hardened  oil  (Talgit); 
3.5  Kilos  caustic  potash  solution  50°  Be"; 

13  Kilos  caustic  soda  solution  37°  Be; 
150  Kilos  mineral  oil  (0.870); 

15  g.  Chinolin  yellow  (fat  soluble). 

3.  Grade  for  lighter  machinery. 

40  Kilos  hardened  oil  (Olinit); 

3.5  Kilos  caustic  potash  solution  50°  Be*; 

13  Kilos  caustic  soda  solution  37°  Be; 

150  Kilos  mineral  oil  (0.870); 

20  g.  Chinolin  yellow  (fat  soluble). 

Brooks  *  describes  a  process  of  manufacturing  hydrogenated  rosin 
having  many  of  the  properties  of  common  rosin  such  as  solubility 
in  varnish  solvents  and  saponifiability  or  soap-making  properties 
but  differing  from  ordinary  rosin  by  possessing  a  substantial  stability 
and  diminished  oxidizability  as  evinced  by  giving  a  lessened  absorp- 
tion of  iodine  or  bromine.  Varnishes  can  be  prepared  from  the 
treated  rosin  which  do  not  crack  and  fissure  upon  standing  and  soaps 
or  soap  compositions,  sizes,  etc.,  may  be  prepared  from  it  which  do 
not  yellow  with  age. 

It  is  stated  that  ordinary  rosin  or  colophony,  although  often  used  in 
the  manufacture  of  cheap  low-grade  varnishes,  enamels  and  the  like,  gives 
varnishes  which,  in  time,  crack  and  fissure  or  "  craze."  Rosin  makes  an  un- 
usually lustrous  varnish  film,  and  if  it  were  not  for  this  lack  of  permanence  it 
would  be  a  highly  desirable  varnish  resin.  In  other  uses,  rosin  displays  the  same 
tendency  to  alteration  and  deterioration  with  time.  Rosin  soaps  are  not  per- 
manent but  become  yellower  and  harder  on  keeping.  In  one  of  the  most  exten- 
sive uses,  sizing  paper,  the  same  tendency  obtains.  This  lack  of  permanence  is 
stated  by  Brooks  to  be  largely  due  to  the  fact  that  rosin  is  an  unsaturated  body 
and,  therefore,  tends  to  oxidize  when  exposed  to  air,  in  the  way  in  which  it  is 
exposed  in  a  varnish  film,  in  a  body  of  soap  or  as  the  sizing  in  paper.  In  the 
case  of  rosin  size  in  paper  the  oxidation  not  only  affects  the  size  itself  but  the 
paper  as  well;  probably  because  of  the  development  of  peroxide,  formic  acid, 
etc.  Rosin-sized  paper,  particularly  if  exposed  to  light  and  air,  in  time  becomes 
friable  and  yellow.  By  combining  or  saturating  the  rosin  with  hydrogen,  a 
material  is  obtained  which  displays  all  the  valuable  properties  of  rosin  as  regards 
the  making  of  high  luster  varnish  films  and  the  preparation  of  soap  while  it  no 

*  U.  S.  Patent  No.  1,167,264,  January  4,  1916. 


404  THE  HYDROGENATION  OF  OILS 

longer  has  the  undesirable  property  of  lack  of  permanence  or  stability  when 
exposed  to  the  air.  This  stabilized  rosin  or  colophony  when  converted  into 
varnishes  is  claimed  to  give  a  high-grade  varnish  in  lieu  of  the  ordinary  low- 
grade  article;  a  varnish  film  which  is  permanent  in  air,  and  at  the  same  time  of 
good  appearance.  It  is  also  adapted  to  make  a  better  grade  of  soap  and  a  higher 
class,  more  permanent  paper  size. 

Brooks  observes  that  abietic  acid,  or  the  acid  of  rosin,  appears  to  hydrogenate 
in  stages,  there  being  a  first  absorption  of  hydrogen  which  is  more  energetic 
than  the  later  absorption.  This  first,  easily  hydrogenating  stage  corresponds  to 
the  highest  oxidizability  and  if  the  hydrogenation  be  carried  only  to  the  end 
of  this  first  stage  the  rosin  .loses  most  of  its  alterability  in  air. 

While  the  addition  of  hydrogen  to  the  rosin  may  be  performed  in  many  ways: 
a  simple  method  of  procedure  is  to  reduce  the  rosin  to  a  fluid  state  by  heat, 
stir  in  3  per  cent  of  freshly-reduced  nickel  and  expose  the  mixture  to  an  atmos- 
phere or  current  of  hydrogen.  Any  suitable  stirring  or  agitating  means  may  be 
used  to  produce  intimate  contact  of  the  mixture  of  rosin  and  catalyst  with  the 
hydrogen  gas.  A  temperature  of  180°  to  230°  C.  is  suitable  for  this  operation. 
The  progress  of  the  reaction  may  be  followed  by  watching  the  gauge  pressure 
where  the  operation  is  performed  under  pressure.  When  the  pressure,  as  indi- 
cated by  the  gauge,  ceases  to  diminish  with  comparative  rapidity,  that  is,  the 
rapidity  of  absorption  of  hydrogen  slackens,  the  first  stage  of  saturation  is  over. 
After  this  time  there  will  be  a  slower  diminution  of  pressure.  The  treatment 
may  be  carried  to  a  point  where  the  iodine  absorption  shows  no  further  sub- 
stantial reduction  on  continuation  of  the  treatment  or  to  the  point  where  the 
iodine  number  disappears  altogether. 

Instead  of  using  nickel,  other  metals  such  as  cobalt,  copper  or  iron  may  be 
employed,  but  these  other  metals  are  not  quite  as  effective  as  the  nickel.  Which- 
ever metal  is  used  it  is  best  reduced  from  an  oxide  formed  from  its  nitrate, 
reduction  being  by  a  current  of  hydrogen  at  a  low  temperature;  a  temperature 
not  markedly  in  excess  of  200°  C.  and  advantageously  lower.  Instead  of  using 
these  metals,  their  oxides  may  be  employed,  but  in  this  event  it  is  desirable  to 
perform  the  treatment  with  hydrogen  at  a  somewhat  higher  temperature,  say 
about  240°  C. 

The  catalyst  may  be  used  with  any  of  the  usual  carriers  such  as  kieselguhr, 
or  asbestos,  etc.,  to  increase  the  contact  surface. 

"  Impregnation  "  with  hydrogen  may  usually  be  accomplished  in  about  three 
hours  at  200°  C.,  using  freshly  reduced  nickel. 

In  lieu  of  simply  melting  the  rosin,  a  solvent  may  be  used  as  a  vehicle  for 
the  rosin  and  catalyst;  such  as  alcohol  or  a  good  grade  of  kerosene. 

Instead  of  using  the  stated  metals,  or  their  oxides,  colloidal  palladium  (or 
palladium  chloride)  or  other  platinum  group  metal,  may  be  used.  Palladium  in 
the  colloidal  or  spongy  condition  is  stated  to  be  an  advantageous  catalyst.  In 
using  colloidal  palladium,  hydrogenation  may  be  performed  at  the  ordinary 
temperature  or  slightly  higher,  the  rosin  in  this  case  being  maintained  in  a  fluent 
condition  by  the  use  of  an  appropriate  solvent,  such  as  alcohol,  benzol,  gasolene, 
toluene,  etc.  Colloidal  palladium  may  be  directly  formed  in  or  added  to  the 
rosin  solution  or  it  may  be  produced  in  an  oily  carrier  and  then  added  to  the 
solution  of  rosin.  Or  a  water  solution  of  colloidal  palladium  may  be  agitated 
with  a  solution  of  rosin  in  a  suitable  solvent  in  the  presence  of  hydrogen  until 
the  desired  degree  of  saturation  is  effected. 


USES  OF  HYDROGENATED  OILS  405 

Similar  resuUs  to  those  given  by  colophony  may  be  obtained  upon  hydrogena- 
tion  of  many  other  resins  known  as  varnish  "  gums  "  and  in  use  for  making 
varnish.  It  is  claimed  that  the  hydrogen  treatment  much  improves  their  sta- 
bility and  quality.  Among  other  resins  which  may  be  improved  by  hydro- 
genation  are  Pontianak  and  guayule  resin. 

When  using  iodine  to  control  the  reaction,  a  convenient  form  of  test  is  the 
Hanus  method  of  determining  the  iodine  number.  Brooks  states  that  ordinarily 
he  carries  on  hydrogenation  till  the  resultant  product  shows  an  iodine  value 
of  20  or  less  by  the  Hanus  method.* 

HYDROGENATED  OIL  IN  THE  TANNING  INDUSTRY 

Hydrogenated  oils  are  now  being  used  by  tanners  for  stuffing 
leather  and  other  purposes.  Fish  and  whale  oil  are  especially  suited 
for  this  purpose.  A  product  low  in  fatty  acids  is  desired,  as  any 
large  amount  of  free,  fatty  acid  is  regarded  by  the  tanner  as  likely 
to  cause  the  leather  to  spue. 

A  paper  by  Lumbard  before  the  American  Leather  Chemists'  Association, 
Chicago,  October  30,  1914,  f  and  presented  by  Dr.  Rogers  contains  the  following 
discussion  on  the  hydrogenation  process  and  refers  particularly  to  leather  man- 
ufacture. 

It  is  everywhere  known  that  those  industries  which  work  up  fats  have  been 
seriously  upset  for  many  years  by  the  considerable  advance  of  prices  of  raw  mate- 
rials. The  rapid  development  in  the  manufacture  of  fats  for  nourishment,  espe- 
cially, has  made  solid  fats  so  scarce  and  expensive  that  the  soap  industry  which 
absolutely  requires  solid  fats  for  the  manufacture  of  solid  toilet  and  household 
soap,  have  found  it  very  difficult  to  get  the  necessary  raw  materials.  As  there 
are  still  large  quantities  of  liquid  fats  obtainable  at  quite  low  prices,  it  has 
consequently  become  a  necessity  to  find  a  chemical  method  for  the  transforma- 
tion of  the  liquid  raw  materials  into  solid  ones.  The  problem  has  been  solved 
by  the  catalytic  method  of  hardening  fats. 

The  liquid  fats  differ  from  the  solid  ones  by  the  low  percentage  of  hydrogen 
of  their  fatty  acids,  by  the  unsaturated  character  which  besides  the  liquid  con- 
dition involves  still  other  properties,  by  the  tendency  to  rapid  oxidation  in  open 
air,  by  the  dark  coloring  and  by  the  disagreeable  fish  odor  of  the  highly  unsat- 
urated fish-oil  fatty  acids  which  hampers  the  possibility  of  employing  fish  oils. 

For  more  than  fifty  years  the  problem  of  hardening  fats  occupied  chemists 
and  manufacturers,  but  none  of  the  many  processes  which  have  been  suggested 
could  be  carried  out  in  practice. 

With  the  development  of  physical  chemistry,  the  science  of  the  "  katalysa- 
toren  "  has  got  footing,  and  after  it  had  been  shown  by  the  experiments  of  the 
French  savants  Sabatier  and  Senderens,  that  by  the  aid  of  nickel  in  a  fine  state 
of  subdivision  it  is  possible  to  join  hydrogen  to  unsaturated  compounds,  W.  Nor- 
mann  found  that  unsaturated  fats  or  fatty  acids,  in  which  finely-divided  nickel 
was  suspended,  could  be  made  to  unite  with  hydrogen.  In  Germany  the  process 
of  Normann  for  a  long  tune  did  not  attract  any  attention,  but  it  was  taken  up 

*See  also  U.  S.  Patent  No.  1,249,050  to  Ellis. 
t  J.  Am.  Leather  Chemists,  Association,  1915,  80. 


406  THE  HYDROGENATION  OF  OILS 

by  the  English  firm  of  J.  Crosfield  &  Sons,  and  perfected  in  a  few  years  to  an 
important  technical  process  which  supplied  in  1906  many  tons  a  day. 

The  German  patent  passed  on  to  the  Naamlooze  Venootschap  Anton  Jurgens, 
who  established  in  1911  the  Germania  Oelwerke,  where  to-day  100  tons  of 
liquid  fat,  mostly  fish  oil,  are  being  hardened  every  day. 

A  great  number  of  patents  have  been  asked  for  the  employment  of  the  nickel 
method,  which,  however,  in  Germany  are  all  dependent  on  the  Normann  patent. 
The  most  known  of  these  processes  is  the  one  of  Wilbuschewitsch.  After  an 
arrangement  with  the  Germania  Oelwerke  they  now  use  their  process  for  the 
manufacturing  of  hardened  oils  for  food  purposes. 

Besides  the  nickel  method,  another  one  developed  from  the  experiments  of 
Paal,  which  used  palladium  as  a  catalyzer.  The  addition  of  hydrogen  in  this 
case  is  done  more  quickly  and  at  a  lower  temperature,  and  the  products  are  very 
satisfactory,  but  in  view  of  the  high  price  of  palladium  competition  with  the 
nickel  method  is  impossible. 

Great  attention  has  been  called  to  a  process  of  Erdmann  and  Bedford,  hi 
which  oxide  of  nickel  is  substituted  for  nickel.  The  oxide  of  nickel  seems  to  be 
more  insensible  toward  the  soilings  of  the  oil  and  the  hydrogen  than  the  metal 
in  fine  distribution.  This  process  has  been  also  perfected  in  England.  A  fac- 
tory in  Germany,  the  Oelwerke  Hydrogen,  will  start  manufacturing  within  a 
short  time.  A  heated  dispute,  which  is  not  yet  decided,  is  carried  on  about  the 
question  whether  in  the  Erdmann  process  also,  nickel  is  the  effective  catalyzer, 
as  is  supposed  by  Normann,  or  whether  the  conception  of  Erdmann  is  right, 
who  says  that  the  oxide  of  nickel  is  being  reduced  to  suboxide,  which  acts  as  a 
catalyzer.  A  German  patent  for  the  nickel  oxide  method  has  just  been  granted, 
after  the  English  patent  has  been  in  force  for  several  years. 

A  number  of  other  processes  are  based  upon  nickel  compounds,  which,  during 
the  treatment  with  hydrogen  are  transformed  to  nickel.  The  method  of  Wim- 
mer-Higgins,  for  the  exploitation  of  which  the  Fettraffinerie  A.  G.  at  Brake  has 
put  up  a  factory,  is  using  especially  formate  of  nickel.  This  method  is  also 
closely  connected  with  the  one  of  Normann. 

The  hardened  fats,  hardened  fish  oils,  linseed  oil  and  cottonseed  oil  are  to-day 
used  to  a  very  large  extent  for  soap  manufacturing,  on  account  of  the  superior 
foaming  properties,  in  conjunction  with  other  fats. 

For  the  manufacturing  of  edible  fats,  the  hardening  of  fats  is  of  utmost 
importance,  because  by  the  aid  of  this  method  it  is  possible  to  use  vegetable  oils 
in  place  of  animal  fats,  after  the  former  have  been  hardened  to  the  proper 
melting-point. 

Manufacturers,  however,  on  principle,  do  not  use  hardened  fish  oil  for  food 
products,  in  order  not  to  give  the  producers  of  natural  butter  any  more  topics 
to  agitate  against  margarine,  although  the  production  of  butter  in  Germany  is 
not  sufficient  by  far  to  cover  requirements. 

In  a  general  discussion  which  followed,  Lumbard  stated  that  the  reason  he 
wanted  to  call  the  Leather  Chemists'  Association's  attention  to  this  product  which 
he  had  brought  over  from  Germany,  was,  that  in  his  trip  to  Germany  he  visited 
many  tanneries,  and  saw  these  products  in  actual  use,  especially  solidified  linseed 
oil,  of  which  they  used  a  good  deal  in  dressing  patent  leather.  They  were  also 
using  quantities  of  solidified  cottonseed  oil.  He  saw  it  being  used  for  replacing 
the  old-fashioned  saponified  linseed  oil,  which  they  used  as  a  top  dressing  in  their 


USES  OF  HYDROGENATED  OILS  407 

patent  leather.  And  they  have  practically  replaced  the  raw  linseed  oil  they  pre- 
viously used  with  this  solidified  linseed  oil.  Cox  said  some  experiments  had  been 
carried  on  with  a  hydrogenated  linseed  oil  from  England.  It  can  be  used  as  a 
fat-liquor  up  to  about  9  per  cent,  and  still  japan  can  be  put  on  top  of  it  without 
decreasing  it,  and  the  japan  not  loosened.  Yocum  inquired  if  it  were  possible  to 
use  hydrogenated  oil  to  the  extent  of  9  per  cent  of  the  weight  of  the  leather  and 
still  be  able  to  japan,  and  in  reply  to  this  Cox  stated  that  the  hydrogenated  oil  is 
sulphonated,  which  affords  a  solid  product  of  comparatively  high  melting-point 
and  could  be  used  in  a  leather  which  is  non-degreased.  Leather  will  carry  9  per 
cent  of  the  oil  and  show  no  objectionable  grease.  Faust  inquired  if  Lumbard  had 
visited  any  harness  leather  tanneries  and  whether  hydrogenated  whale  oil  was 
being  used  as  a  stearine  substitute  in  Germany.  To  this  Mr.  Lumbard  responded 
that  it  was  not  being  used  exactly  as  a  stearine  substitute,  but  to  replace  many  of  the 
oils  such  as  moellon.  In  conjunction  with  stearines  and  tallow  it  has  better  carry- 
ing qualities,  absorbing  and  carrying  the  greases  in  better,  so  the  tanners  stated, 
and  it  leaves  the  flesh  very  clean.  It  has  been  adopted  for  dressing,  for  instance, 
on  satchel,  bag  and  case  leathers,  because  in  dressing  with  it,  it  does  not  run.  It 
is  about  of  the  consistency  of  a  very  heavy  butter,  and  when  it  is  subjected  to  heat 
becomes  limpid.  They  then  mix  it  with  a  little  sulphonated  oil  to  make  it  flow 
and  when  the  leather  is  hung  on  the  hooks  they  claim  that  it  does  not  drip,  that 
the  absorption  of  the  oil  is  clean  and  clear,  and  that  it  does  not  run  to  the  skirts 
as  so  many  free-running  oils  do.  So  on  all  those  harder  leathers  it  has  been  used 
to  a  great  extent,  and  also  on  harness  leather.  Cox  staled  that  with  this  oil  it  is 
possible  to  make  an  emulsion  and  take  sole  leather  of  very  light  color,  dip  the  leather 
into  it,  and  have  the  leather  dry  out  without  any  loss  in  color.  Saxe  made  the 
inquiry  whether  fish  oil  or  vegetable  oil  was  preferred  for  patent  leather  and  Lum- 
bard stated  that  fish  and  linseed  oil  were  preferred  to  cottonseed  oil,  the  reason 
given  being  that  the  cottonseed  oil  hardened  more  than  other  oils.  The  most  satis- 
factory oil  of  all  is  the  hardened  fish  oil.  In  answer  to  an  inquiry  by  Mr.  Yocum 
regarding  the  possibility  of  sulphonating  the  oil  and  then  hardening  it  to  bring  it 
up  to  the  requisite  condition,  Lumbard  stated  that  in  Germany  it  was  the  custom 
to  blend  hardened  oil  with  sulphonated  oil  to  produce  an  emulsion  and  use  it  in  that 
form  as  a  fat  liquor.  Cox  stated  that  it  was  perfectly  possible  to  take  one  part 
of  the  sulphonated  hydrogenated  product,  combine  it  with  four  parts  of  a  fat  such 
as  stearine,  melted,  and  have  it  form  an  emulsion,  then  put  the  leather  in  it,  hang 
up  while  still  wet,  and  the  stock  would  come  out  without  any  discoloration. 
Lumbard  stated  that  what  interested  most  of  the  German  tanners  in  this  product 
is  the  fact  that  when  combined  with  the  sulphonated  oil,  the  linseed  oil  being  a  very 
drying  oil,  will  carry  into  the  leather  and  it  leaves  the  surface  absolutely  clean  and 
free  from  any  fats  that  may  come  up  during  the  process  of  baking  in  the  ovens 
Ordinarily  unless  the  leather  is  degreased,  the  first  coat  has  a  tendency  to  peel. 
They  do  not  experience  any  of  those  difficulties  in  the  use  of  this  hardened  linseed 
oil.  Yocum  inquired  if  hydrogenated  linseed  oil  still  retained  the  property  of 
drying  and  if  it  could  be  boiled  into  a  sweetmeat  or  varnish,  to  which  Lumbard 
responded  that  they  did  not  use  the  hydrogenated  linseed  oil  for  boiling  varnish. 
When  this  oil  is  blended  with  a  sulphonated  fish  oil,  which  they  use  considerably 
in  conjunction  with  it,  he  said  it  seems  to  lose  considerable  of  the  oxidizing  effect, 
that  the  original  linseed  oil  would  have.  It  leaves  the  surface  very  clean.  The 
oil  does  not  flow  out,  it  does  not  come  out  in  the  heat  of  the  ovens,  especially  under 


408  THE  HYDROGENATION  OF  OILS 

a  temperature  of  140  degrees,  to  which  they  subject  leather  in  their  ovens.  They 
follow  up  the  primary  coat  with  a  collodion  coat,  and  it  is  said  that  the  collodion 
coat  adheres  to  the  sweetmeat  coat  better  where  they  use  the  solidified  oil  than 
where  they  use  the  free  oil  in  fat-liquoring. 


GREASES  FOR  STUFFING  HARNESS  LEATHER,  BELTING  AND  OTHER 

HEAVY  LEATHER 

For  stuffing  heavy  leather,  such  as  belting  and  harness  leather, 
various  greases  are  employed,  tallow  being  frequently  used  for  the 
purpose.  The  heavier  grades  of  mineral  oil  are  sometimes  added  to  the 
stuffing  grease.  Leather  of  this  character  requires  from  10  to  30 
per  cent  or  more  of  stuffing  fat  and  the  general  shortage  of  low  priced 
fats  renders  any  new  source  of  fatty  material  of  interest.  Hence 
tanners  have  experimented  extensively  with  hydrogenated  oils,  with 
generally  promising  results.  The  most  useful  fat  is  one  having  a 
melting-point  of  about  125°  F.  and  containing  not  in  excess  of  2  per 
cent  of  free  fatty  acid.  With  higher  percentages  of  fatty  acid  there 
is  danger  that  the  leather  may  spue. 

PREPARATION  OF  FATTY  ACIDS 

Starrels  *  prepares  fatty  acids  by  hardening  a  fatty  oil  to  a  high 
melting-point,  as,  for  example,  to  about  60°  or  62°  C.,  and  an  iodine 
number  of  from  zero  to  2  and  thereby  substantially  completely  con- 
verting the  olein  into  stearine,  also  forming  various  isomers  of  high 
melting-point. 

The  material  is  saponified  by  the  Twitchell  process  or  any  of  the  other  fat- 
splitting  processes  yielding  glycerine  and  high  melting-point  fatty  acids.  The 
latter  mixture  is  then  dissolved  in  a  solvent  medium,  as,  for  example,  alcohol 
or  gasoline,  and,  on  cooling,  the  free  fatty  acids  are  separated  in  a  state  of  purity, 
leaving  in  solution  the  greater  part  of  the  coloring  agents.  An  example  is  the 
following:  Corn  oil  was  hydrogenated,  using  nickel  catalyzer,  until  the  melting- 
point  was  about  62°  C.  It  was  then  subjected  to  the  Twitchell  process  and  the 
fatty  acids  obtained.  These  were  brown  in  color.  Approximately  equal  parts 
of  denatured  alcohol  and  the  fatty  acid  were  incorporated  and  heated  to  form  a 
homogeneous  solution  which  takes  place  rather  readily  at  temperatures  approach- 
ing the  boiling-point  of  alcohol  as  the  fatty  acid  is  relatively  soluble  in  alcohol. 
The  solution  was  cooled  until  practically  all  of  the  fatty  acid  had  separated, 
when  the  material  was  pressed  and  a  brown  extract  containing  the  hydrocarbons 
and  coloring  matters  was  removed  leaving  a  white  fatty  acid  of  very  high  sapon- 
ification  value  and  acid  number  showing  that  the  unsaponifiable  material  formed 
by  hydrogenation  had  been  eliminated. 

*  U.  S.  Patent  No.  1,209,512,  December  19,  1916. 


USES  OF  HYDROGENATED  OILS  409 

Proceeding  along  similar  lines  the  fatty  acids  of  cottonseed,  fish,  whale  and 
other  vegetable  or  animal  oils  may  be  treated  to  form  high-grade  fatty  acids 
suitable  for  the  manufacture  of  first-class  toilet  soaps. 

According  to  a  method  of  the  Renter  Process  Co.,*  in  the  pro- 
duction of  fatty  acids  by  boiling  glycerides  with  organic  catalytic 
hydrolyzers,  the  hydrolysis  is  effected  in  a  number  of  stages,  in 
each  of  which  stages  a  fraction  of  the  total  amount  of  hydrolyzer 
is  added,  the  mixture  being  allowed  to  settle  after  each  boil  and  a 
dark-colored  intermediate  layer  of  impurities  is  removed,  after  which 
more  hydrolyzer  is  added  and  boiling  resumed.  Air  is  excluded  from 
the  saponification  tank.  The  fatty  acids  thus  produced,  and  soap 
and  candles  made  therefrom,  after  aging  for  ten  days  after  making, 
do  not  darken  substantially  in  color  on  exposure  to  air  and  light. 
Glycerides  used  in  this  process  may  be  the  following,  separately  or 
collectively:  Beef  and  mutton  tallows;  horse,  hog,  and  butter  fats 
and  their  greases;  whale,  menhaden,  fish,  cocoanut,  pea"nut,  linseed, 
cottonseed,  palm,  palm-kernel,  and  soya-bean  oils;  and  the  hydro- 
genation  products  of  corn  oil,  linseed  and  cottonseed  oils,  fish  oil,  etc. 

Schauth  f  calls  attention  to  the  advantages  of  the  ordinary  Varren- 
trapp  reaction  and  notes  that  while  the  hydrogenation  process  pro- 
duces fats  which  can  be  employed  in  lathering  soaps  only  by  the 
addition  of  other  fats  and  fatty  acids  that  the  product  obtained  by 
the  Varrentrapp  reaction  is  more  readily  available  in  soap  making. 
He  also  suggests  that  the  hydrogen  formed  during  the  Varrentrapp 
reaction  be  used  for  hydrogenation  purposes. 

Highly  hardened  oil  such  as  a  thoroughly  hardened  cottonseed 
oil  is  used  by  Ellis  J  to  produce  a  flatting  effect  in  paint  composi- 
tions so  that  the  surface  will  dry  to  a  matt  finish. 

Hydrogenated  castor  oil  is  used  by  Cordes  §  as  an  insulating  or 
impregnating  material  for  telephone  condensers. 

In  manufacturing  these  condensers,  long  strips  of  paper  are  laid  on  strips  of 
tin-foil,  the  two  strips  are  then  rolled  up,  and  the  coils  thus  formed  are  pressed 
into  a  rectangular  shape  and  dried  either  with  or  without  the  use  of  a  vacuum. 
The  coils  of  paper  and  tin-foil  are  then  mounted  in  frames,  the  frames  with 
the  coils  thereon  are  placed  in  a  vacuum-impregnating  receptacle  containing  the 
hydrogenated  castor  oil  and  the  coils  are  heated,  for  which  purpose  the  recep- 
tacle has  a  heating  jacket  which  receives  steam  at  a  pressure  of  about  two 
atmospheres.  The  molten  fat  is  in  this  way  caused  to  penetrate  between  the 
paper  and  the  tin-foil  and  the  moisture  is  expelled  by  the  heat  in  the  form  of 

*  British  Patent  No.  9,394,  June  26,  1915. 
t  Chemical  Eng.  and  Mfgr.,  Vol.  XXIV,  1916,  204. 
j  U.  S.  Patent  No.  1,173,183,  February  29,  1916. 

§  U.  S.  Patent  No.  1,241,926,  October  2,  1917.  See  also  Nos.  1,276,507,  1,276,508  and 
1,276,509  issued  August  20,  1918  to  Ellis, 


410 


THE  HYDROGENATION  OF  OILS 


bubbles.  The  vessel  is  subsequently  sealed  hermetically,  and  the  extraction  of 
moisture  continues  until  the  last  trace  has  been  removed  from  the  paper,  this 
part  of  the  process  occupying  from  two  to  four  hours.  After  the  moisture  has 
been  thoroughly  extracted,  cold  water  is  introduced  into  the  jacket.  Owing  to 
the  high  dielectric  properties  of  the  impregnating  material,  it  is  possible  to 
obtain  the  same  effects  with  condensers,  which  are  only  half  as  large  as  those 
necessary  with  the  use  of  paraffin. 

In  a  study  of  corn  oil  with  reference  to  its  use  as  a  substitute 
for  olive  oil  in  various  unctuous  preparations  such  as  liniments, 
ointments,  cerates,  plasters  and  oleates,  Lackey  and  Sayre  inves- 
tigated the  hydrogenation  of  corn  oil.*  Apparatus  was  used  as 
shown  in  Fig.  546. 


Cross  Section, 
FIG.  546. 

Comparative  tests  on  the  hydrogenation  of  corn  oil  and  similar  oils  of  about 
the  same  iodine  value  were  made.  Nickel  oxide  was  used  as  the  source  of  cata- 
lytic material.  A  temperature  of  about  200°  C.  was  used  with  hydrogen  at 
50  Ib.  pressure.  In  six  hours  time  a  product  was  obtained  from  corn  oil  melting 
at  about  36°  C.  The  following  table  shows  comparative  results  with  cottonseed 
and  corn  oil: 


COTTONSEED  OIL. 

CORN  OIL. 

Time,  Hours. 

Melting-point,  °  C. 

Time,  Hours. 

Melting-point,  °  C. 

6 

35 

5| 

31 

10 

39 

7 

34 

7 

35 

7 

33 

3 

29 

3| 

23 

*  J.  Am.  Pharm.  Assn.,  Vol.  VI,  April,  1917,  349. 


USES  OF  HYDROGENATED  OILS  411 

It  is  noted  by  Lackey  and  Sayre  that  the  presence  of  the  small  amount  of 
nickel  remaining  in  the  fat  after  filtration  from  the  catalyzer  is  not  of  sufficient 
moment  to  interfere  with,  or  be  objectionable  in,  making  most  of  the  unctuous 
preparations  referred  to.  One  merit  of  the  hydrogenated  product  is  its  keeping 
qualities.  Lackey  and  Sayre  have  kept  samples  of  hydrogenated  corn  oil  for 
over  a  year  which  have  not  shown  the  least  indication  of  rancidity. 

Hydrogenated  corn  oil  when  well  hardened  possesses  the  property  of 
expanding  on  passing  from  the  molten  to  the  solid  state  and  when  run 
into  barrels  and  allowed  to  solidify  this  form  of  hard  fat  has  been 
observed  to  break  the  hoops  of  the  barrels  during  the  period  of  expan- 
sion. In  this  respect  com  oil  resembles,  in  a  lesser  degree,  highly 
hardened  Chinese  wood  oil.  (See  page  361). 

Fox  *  notes  that  practically  all  the  semi-drying  oils  (except  Chinese  wood  oil) 
are  capable  of  use  for  lubricants,  as  they  can  be  hydrogenised  and  converted  into 
non-drying  oils.  He  prepared  a  lubricating  oil  from  hydrogenised  soya  bean  oil 
mixed  with  14  per  cent  of  mineral  oil.  A  lubricating  grease,  similarly  made,  was 
used  in  the  gearbox  of  a  motor  car  for  nearly  a  year. 

Ellis  f  incorporated  hydrogenated  oil  and  pulverulent  material. 
The  product  may  take  either  of  two  forms.  (1)  a  solid  cake  or  semi- 
solid  coherent  mass  and  (2)  a  comminuted  or  pulverulent  product. 
The  solid  cake  may  be  used  for  a  variety  of  purposes  such  as  buffing 
and  grinding,  lubricating,  polishing  and  the  like.  A  lubricating  powder 
may  be  made,  for  example,  from  equal  weights  of  hydrogenated  oil 
and  graphite.  A  buffing  or  grinding  composition  may  be  produced 
from  hydrogenated  oil  and  an  abrasive  powder  such  as  crocus  or  car- 
borundum and  emery.  A  tailor's  chalk  may  be  made  by  melting 
hydrogenated  cottonseed  oil  of  m.p.  60°  C.  with  a  quantity  of  talc. 
Products  in  the  powdered  form  containing  hydrogenated  oil  and  carbo- 
hydrates may  be  used  for  edible  purposes. 

Referring  to  the  imports  at  Pacific  ports  of  dog-fish,  halibut,  salmon,  sardine, 
shark,  tuna  fish,  candle  fish,  walrus,  whale,  seal  and  porpoise  oils,  Sadtler  t  states  such 
oils  have  an  added  value  since  the  general  application  of  the  hydrogenation  process 
as  they  can  be  changed  into  hardened  fats  valuable  to  the  soap  and  glycerine 
manufacturer. 

*  J.  S.  C.  I.  1918,  304R. 

t  U.  S.  Patents  Nos.  1,276,507,  1,276,508  and  1,276,509,  August  20,  1918. 

t  Chem.  Met,  Eng.  1918,  558. 


CHAPTER   XVII 
HYDROGENATION   PRACTICE 

Whether  or  not  the  plant  is  to  treat  animal  or  vegetable  oils,  or 
fish  oil,  the  following  general  procedure  may  be  laid  down  for  guidance 
in  the  equipment  and  operation  of  a  hydrogenating  works. 

The  starting  point  is,  perhaps,  the  preparation  of  catalyzer.  Of 
course  the  procedure  employed  for  its  preparation  depends  on  the 
type  of  catalyzer  selected.  Suppose  nickel  be  chosen  as  the  active 
material,  to  be  used  on  a  suitable  carrier  or  supporting  base.  To  this 
end  a  solution  of  a  nickel  salt,  such  as  the  nitrate  or  sulfate,  is  mixed 
in  vats  with  the  support,  in  the  presence  of  a  precipitant,  or  the 
latter  is  subsequently  added,  and  the  material  is  well  agitated.  Solu- 
ble salts  should  then  be  removed  by  washing  and  the  material  dried. 
These  operations  may  take  place  in  a  filter  press  supplied  with  air 
under  pressure.  The  caked  product  should  be  ground  in  a  ball  or 
pebble  mill  until  resolved  into  a  fine  powder. 

The  catalyzer  is  now  ready  for  reduction,  which  should  be  per- 
formed with  extreme  care  as  the  entire  oil-hardening  process  depends 
on  the  efficiency  of  the  catalyzer.  A  simple  and  efficient  type  of 
catalyzer-reducing  device  is  represented  by  Fig.  55.  A  is  a  brick 
structure  which  contains  the  reducing  drum  B.  The  latter  is  rotated 
by  means  of  the  sprocket  C.  E1E2  are  stuffing  boxes  which  admit 
of  rotating  the  drum  without  disturbing  the  gas  inlet  and  outlet. 
The  catalyzer  is  admitted  and  withdrawn  through  the  gate  G.  The 
drum  is  filled  about  two-fifths  full  of  the  catalyzer  and  hydrogen 
passed  in.  When  tests  for  oxygen  show  that  all  the  air  has  been 
expelled  the  drum  is  heated  to  a  temperature  not  exceeding  360°  C. 
During  reduction  the  hydrogen  is  passed  through  at  a  considerable 
rate  in  order  to  remove  the  steam  formed,  thus  reducing  the  partial 
pressure  of  the  latter  and  facilitating  the  reduction  of  the  nickel 
oxide  or  hydrate.  The  gases  issuing  from  the  exit  side  of  the  drum 
may  pass  through  a  water  seal  and  after  purification  may  be  returned 
to  the  gas  holders  to  be  used  again.  When  the  issuing  gases  are  found 
to  contain  no  steam  the  reduction  is  complete,  the  heating  is  dis- 
continued and  the  catalyzer  allowed  to  cool  in  a  current  of  hydrogen. 

412 


HYDROGENATION  PRACTICE 


413 


After  cooling  the  catalyzer,  the  hopper  shown  in  Fig.  55  is  coupled 
to  the  flange  of  the  gate  G.  The  bottom  of  the  hopper  dips  below  the 
surface  of  oil  contained  in  a  receptacle  beneath.  Hydrogen  is  passed 
in  at  the  valve  J  and  the  air  is  thereby  expelled  from  the  hopper. 
The  valve  of  the  reducing  drum  is  now  opened  and  the  catalyzer 
allowed  to  fall  into  the  oil  with  which  it  should  be  thoroughly  mixed. 
Thus  the  catalyzer  is  effectively  sealed  from  the  air. 


FIG.  55. 


This  method  of  abstracting  catalyzer  from  the  reducing  drum  pre- 
vents oxidation  of  the  nickel  which  occurs  to  a  greater  or  less  extent 
when  the  catalyzer  is  withdrawn  in  contact  with  the  air. 

The  catalyzer  in  oil  may  then  be  transferred  to  a  large  agitating 
tank  in  which  oil  is  added  in  sufficient  quantity  to  make  the  mixture 
contain  the  correct  percentage  of  catalyzer.  The  contents  are  thor- 
oughly agitated  and  transferred  to  the  hydrogenator  where  the  actual 
hydrogenation  takes  place. 

Tall  iron  tanks  may  be  used  for  this  purpose,  one  type  of  which  is 
shown  in  Fig.  56.  The  air  in  the  hydrogenator  is  displaced  by  means 
of  hydrogen  and  the  mixture  of  catalyzer  and  oil  pumped  from  the 


414 


THE  HYDROGENATION  OF  OILS 


agitator  A  into  the  hydrogenator  C.  The  contents  of  the  hydro- 
genator  are  heated  to  a  temperature  of  175°  to  190°  C.  by  means  of 
superheated  steam  or  hot  oil  coils,  the  latter  being  preferable  owing 
to  the  danger  of  leakages  of  steam  into  the  chamber.  The  tempera- 
ture of  the  contents  of  the  hydrogenator  should  be  registered  by 
means  of  a  reliable  thermometer,  preferably  a  recording  pyrometer. 


FIG.  56. 

The  oil  and  catalyzer  in  the  hydrogenator  are  circulated  by  means 
of  the  rotary  pump  E,  which  takes  the  liquid  from  the  bottom  of  the 
hydrogenator  and  pumps  it  through  the  inductor  I  where  hydrogen 
drawn  from  the  gas  space  at  the  top  of  the  hydrogenator  is  mixed  with 
the  oil.  CK  is  a  check  valve  to  prevent  oil  from  entering  the  tank 
through  the  suction  tube  in  the  event  of  the  inductor  suction  nozzle 
becoming  flooded.  The  mixture  of  oil,  catalyzer  and  hydrogen  is 
ejected  through  the  distributor  D  at  the  bottom  of  the  hydro- 
genator. 

The  hydrogen  inlet  is  provided  with  a  safety  device  M  and  a 
pressure  gauge  P3. 


HYDROGENATION  PRACTICE  415 

The  pressure  maintained  in  the  hydrogenator  is  variable  according 
to  the  oil  under  treatment  and  may  range  from  atmospheric  or  less 
up  to  about  25  pounds.*  The  difference  in  the  readings  of  the  pres- 
sure gauges  P\Pt  registers  the  suction  of  hydrogen  at  the  suction  nozzle 
of  the  inductor.  Samples  of  oil  may  be  withdrawn  from  time  to  time 
from  the  outlet  Q.  When  the  sample  indicates  that  the  oil  has  the 
required  hardness  the  hydrogenator  is  emptied  through  the  outlet  V 
and  the  contents  are  run  into  large  tanks  which  are  heated  by  means 
of  steam  coils.  From  these  tanks  the  mixture  of  oil  and  catalyzer  is 
pumped  into  filter  presses  where  the  catalyzer  is  removed.  The  oil 
is  finally  run  into  cooling  tanks  where  it  solidifies  to  a  hard  fat  ready 
to  be  made  into  lard  compound,  soap  or  other  product. 

The  transformation  to  olein  of  the  glycerides  of  linoleic  and  linolenic 
acids  or  other  highly  unsaturated  acids  usually  does  not  result  in  any 
marked  change  in  the  titer.  As  these  bodies  sometimes  are,  to  a  con- 
siderable extent,  transformed  into  olein  before  olein  becomes  stearin, 
hydrogen  will  be  absorbed  by  the  oil  without  hardening,  to  a  degree 
dependant  on  the  proportion  of  these  highly  unsaturated  bodies 
present.  Often  an  hour  or  more  is  needed  to  bring  an  oil  to  the 
*'  olein  stage,"  after  which  hardening  will  progress  rapidly. 

Of  course,  the  method  given  above  is  capable  of  many  modifications, 
as  oils  of  different  character  require  different  treatment  and  in  con- 
sequence oftentimes  call  for  equipment  which  varies  considerably 
from  that  given  by  way  of  illustration.  Catalyzers  vary  a  good  deal 
in  their  properties,  and  conditions  which  are  suitable  for  nickel  in 
some  of  its  forms  will  not  answer  for  palladium.  A  much  lower 
temperature  usually  suffices  when  using  the  latter  metal  as  a  catalytic 
substance. f 

A  simple  type  of  converter  now  extensively  used  is  shown  in  Fig.  56a. 
It  consists  of  a  closed  tank  equipped  with  a  steam  coil  and  stirrer. 
The  vessel  is  charged  with  oil  and  catalyzer  and  the  charge  is  heated 
to  the  requisite  temperature  when  hydrogen  is  introduced  by  the  small 
pipes  in  the  bottom  of  the  apparatus.  The  oil  is  stirred  vigorously 
during  the  operation.  Heat  is  developed  in  hydrogenating  fatty  oils 

*  One  of  the  difficulties  met  with  in  the  handling  of  hydrogen  has  been  the  loss 
by  leakage  of  the  gas.  Under  pressure  and  at  a  temperature  of  150°  or  200°  C., 
hydrogen  is  surprisingly  penetrating.  Autoclaves  with  welded  seams  are  desirable 
for  high-pressure  and  high-temperature  work.  Moving  parts  should  be  avoided  as 
far  as  possible. 

t  Reference  is  made  to  the  chapter  on  catalyzers  which  gives  much  detailed 
information  on  the  subject.  Attention  is,  however,  called  to  the  existence  of  several 
patents  covering  certain  forms  of  catalytic  preparations. 


416 


THE  HYDROGENATION  OF  OILS 


and  when  a  considerable  quantity  of  oil  is  being  hardened,  the  heat 
of  reaction  may  be  not  only  sufficient  to  maintain  the  batch  at  the 
reacting  temperature  but  may  even  cause  the  temperature  to  rise  too 
high,  so  that  cooling  is  needed.  This  is  especially  noticeable  with 


FIG.  56a, 

freshly-prepared  catalyzer.  Sometimes  preliminary  heating  by  steam 
to  100°  to  120°  C.  suffices  to  start  the  reaction  and  the  temperature 
rises  rapidly.  At  170°  to  180°  C.  water  may  be  passed  through  the 
coil  to  prevent  overheating. 


HYDROGENATION  PRACTICE 


417 


FIG.  566.— Shriver  Filter  Press  for  Filtering  Hardened  Oil. 

The  filtration  of  oil  to  remove  finely-divided  nickel,  especially  when 
in  a  colloidal  or  partially  colloidal  condition,  is  aided  by  the  addition 
of  fuller's  earth,  silex  or  some  similar  bulking  material.* 

*  U.  S.  Patent  to  Ellis,  No.  1,158,664,  Nov.  2,  1915. 


CHAPTER  XVIII 
THE  HYDROGENATION  OF  PETROLEUM 

THE  hydrogenation  of  the  unsaturated  constituents  of  petroleum  has 
proved  to  be  a  fascinating  subject  of  research  by  chemists  and  the  literature 
on  this  topic  has  been  greatly  augmented  of  late.*  See  pages  11  and  21 
for  earlier  data. 

The  results  of  experiments  by  Winkler  f  on  the  problem  of  motor  gaso- 
line are  of  interest.  Winkler  observes  that  California  petroleum  is  one  of 
the  large  sources  for  gasoline,  and  yet  that  probably  80  per  cent  of  it  is 
too  thick  for  any  explosive  mixture  and  "  a  sootless  burn  "  in  the  cylinder. 
To  depolymerize  the  heavy  hydrocarbon  oils  down  to  their  simplexes 
somewhat  analogous  to  the  depolymerization  of  synthetic  rubber  back 
to  isoprene— the  following  experiments  were  carried  out: 

First,  by  way  of  explanation,  "  cracking  "  of  these  oils  by  mere  superheating,  he 
states,  has  proved  totally  unprofitable  in  California  factories;  and  so  have  all  kinds 
of  pyrogenic  experiments  in  his  laboratory  (i.e.,  passing  the  vapors  with  hydrogen 
through  hot  tubes  containing  various  metals).  The  results  have  not  shown  promise 
as  the  products  go  largely  into  the  sludge  in  refining,  and  have  penetrating  odors. 
The  oils  show  great  tendency  to  thicken  when  heated,  especially  in  contact  with 
various  substances,  as  air,  alkali,  concentrated  sulphuric  acid,  and  various  salts,  as 
aluminum  chloride.  The  best  results,  he  notes,  are  obtained  by  distillation  in  an 
atmosphere  of  hydrogen.  In  addition  to  the  unsaturated  cyclic  bodies,  and  the 
sulphur  and  nitrogenous  compounds,  these  oils  contain  benzol  ring  bodies  with  side 
chains,  as  the  mesitylenes,  forming  the  turpentine  substitutes.  Asphalt  occurs 
therein  as  a  colloid,  t  and  is  eliminated  at  the  start  by  fractional  steam  distillation. 
Winkler 's  experiments  are  as  follows: 

1.  Effect  of  Corona.  A  glass  tube  2^  in.  diameter  by  3|  ft.  long,  wrapped  with 
wire  gauze,  with  a  ^-in.  copper  rod  suspended  co-axially  through  its  centre,  was  used 
as  a  hot  vapor  chamber,  while  at  the  same  time  the  inside  rod  and  outside  gauze 
were  kept  at  a  potential  of  from  25,000  to  30,000  volts  by  dynamo  and  high  potential 
transformer.  When  the  room  was  darkened,  a  continuous  bright  bluish  glow  was 
evident  throughout  the  tube,  i.e.,  a  corona.  Through  this  glow  (air  removed)  various 
California  heavy  distillates  were  distilled  repeatedly,  with  a  large  excess  of  hydrogen 
(dry  and  moist),  the  object  of  the  corona  being  to  ionize  the  hydrogen.  (The  dielec- 

*  Cf .  Moore  and  Egloff  on  "Fats  and  Fatty  Acids  from  Petroleum,"  Met.  and  Chem. 
Eng.,  1918,  309.  See  also  Bureau  of  Mines,  Bulletin  149,  Bibliography  of  Petroleum, 
by  Burroughs. 

f  J.  Franklin  Inst.,    178,  1914,  97. 

%  Z.  Ang.  Ch.,  1913,  609. 

418 


THE  HYDROGENATION  OF  PETROLEUM       419 

trie  constants  of  hydrogen  and  hydrocarbon  vapors  and  air  were  found  to  be  not 
very  different.)  Practically  no  change  could  be  detected  in  the  oils  after  repeated 
slow  distillations  through  the  above  chamber. 

2.  Effect  of  Arc.     The  Birkeland-Eyde  process  was  applied  to  these  oils  in  an 
atmosphere  of  hydrogen.     The  oils,  both  liquid  and  gaseous,  were  passed  through 
with  increasing  speed,  to  shorten  the  time  in  the  arc.     The  carbons  were  hollow, 
and  hydrogen  was  passed  inward  through  both.     They  were  kept  cool  by  a  water 
jacket.     The  results  were  variable,  but  in  every  case  the  oils  were  reduced  to  non- 
condensable  gases  and  a  cloud  of  fine  carbon. 

3.  Effect  of  Steam  and  Aluminum  under  Pressure.     Very  fine  aluminum  dust  was 
mixed  with  various  heavy  California  oils  to  a  " suspension,"  and  these  mixtures 
subjected  to  a  pressure  of  110  Ib.  per  square  inch  with  steam  in  a  heavy,  specially 
constructed  retort.     They  were  also  .agitated,  and  at  the  same  time  heated  to 
various   temperatures  (indicated   by  thermometer)  up   to   their   cracking  points. 
The  purpose  of  the  aluminum  and  steam  was  to  generate  nascent  hydrogen  within 
the  oil.     A  variety  of  attempts  indicated  no  success.     The  aluminum  was  not  amal- 
gamated. 

4.  Effect  of  Reduced  Nickel  Oxide  and  Hydrogen  on  the  Aerated  Oil.     According  to 
Charitschkoff,  better  results  at  "  cracking  "  Russian  petroleum  were  obtained  by 
first  oxidizing  the  oil.*     Heavy  California  oils  were  heated  and  aerated  (by  drawing 
air  through  them)  for  two  or  three  days,  to  oxidize  them  and  to  generate  petroleum 
acids  (the  purpose  of  this  oxidation  also  being  to  introduce  carboxyl  groups,  with 
the  possibility  of  splitting  out  water  with  the  hydrogen  afterwards,  and  leaving  the 
rest  of  the  broken  molecule  to  unite  with  the  excess  hydrogen).     The  aerated  oils 
were  subjected  to  the  action  of  reduced  nickel  oxide  and  hydrogen  (said  to  be 
least  sensitive  to  sulphur  compounds,  f    but  without  success.     Iodine  was  substi- 
tuted for  the  nickel  oxide  with  no  better  results. 

5.  Effect  of  Rhodium  Black  and  Hydrogen.     First,  active  platinum  black,  made 
according  to  the  Loew  process,  \  has  been  shown  to  be  a  good  catalyst  to  hydrogenate 
pure  benzol  and  pure  benzine.     It  is,  however,  poisoned  by  sulphur  bodies. §     Cal- 
ifornia oils  contain  sulphur,  and  do  not  hydrogenate  under  these  conditions. 

Bredig  has  shown  that  rhodium  metal  acts  as  a  catalyst  to  break  down  formic  and 
acetic  acids  to  hydrogen  and  carbon  dioxide,  etc.,  and  that  sulphur  bodies  are  favor- 
able to  its  activity. 1 1  Rhodium  black  was  made  (by  the  Loew  process),  and  tried 
out  on  California  oils  under  parallel  conditions,  but  failed  to  hydrogenate  in  the 
least. 

Snelling^f  is  able  to  produce  a  high-grade  petroleum,  yielding  substantial 
proportions  of  gasoline  and  kerosene  fractions,  from  low-grade  crude  oils 
and  petroleum  products  such  as  gas  oil,  by  heating  them  to  a  temperature 
such  that  the  vapors  evolved  will  produce  an  added  pressure  of  at  least 
400  Ib.  per  square  inch,  the  quantity  of  liquid  in  the  container  being  such 

*  "Petroleum,"  1913,  748. 
t  Z.  angew.  Chem.,  1913,  561-606. 
I  Ber.  23,  289. 
§  Ibid.,  45,  1471. 

||Oest.  Ch.  Ztg  ,  No.  14,  1911,  266. 

1  British  Patent  No.  18,419,  Aug.  7,  1914;  Chem.  Abs.,  1916,  388.  Cf.  O.  P  &  Drug 
Reporter,  Apr.  5,  1915,  33.  Gasoline  from  Synthetic  Crude  Oil,  by  Snelling. 


420  THE  HYDROGENATION  OF  OILS 

that  it  occupies  not  less  than  one-tenth  and  not  more  than  seven-tenths 
of  the  total  capacity  of  the  container. 

The  operation  may  be  effected  in  the  presence  of  a  catalyst  such  as  colloidal  graph- 
ite, colloidal  carbon  (formed  by  producing  an  arc  between  carbon  points  immersed 
in  the  oil),  or  nickel  or  other  metal  in  the  colloidal  form,  or  in  the  presence  of  gases 
and  vapors  such  as  hydrogen,  natural  gas,  ethylene,  oil  gas,  water-gas,  or  steam. 
Temperatures  in  excess  of  380°  and  below  600°,  preferably  between  400  and  500°, 
are  employed. '  Pressures  between  600  and  800  Ib.  per  square  inch  are  preferred, 
though  a  pressure  of  2400  Ib.  per  square  inch  may  be  employed.  According  to  one 
method  of  treatment,  the  oil  is  heated  until  the  pressure  reaches  800  Ib.  per  square 
inch,  and  is.  then  allowed  to  cool.  The  permanent  gases  are  allowed  to  escape, 
and  may  be  used  for  heating  or  for  making  propane  or  butane.  The  oil  is  fractionated 
up  to  150°,  and  the  residue  is  subjected  to  a  further  treatment. 

According  to  Oildom,*  petroleum  and  other  heavy  hydrocarbons  are 
cracked  by  heating  them  in  a  cracking-still,  together  with  a  catalyst,  such 
as  finely-divided  nickel,  and  hydrogen  or  purified  water-gas,  with  violent 
agitation. 

The  vapors  may  be  passed  through  a  chamber,  containing  a  finely-divided  catalyst, 
such  as  asbestos,  coated  with  nickel,  on  their  way  to  the  condenser. 

The  heavy  hydrocarbon  is  first  purified  from  asphalt,  sulphur,  arid  other  catalyst 
poisons,  and  is  passed  from  the  store-tank,  together  with  hydrogen  from  a  reservoir 
along  a  pipe,  where  it  mixes  with  nickel  from  a  shot-flask  device,  entering  the  still 
through  a  rose.  The  still  is  fitted  with  an  agitator.  The  distillation  is  effected  at 
about  300°  C.  and  under  a  pressure  of  5-1000  Ib.  per  square  inch  regulated  by  a 
weighted  valve.  The  gases  which  escape  from  the  condenser  are  burnt  under  the 
still,  or,  if  rich  in  hydrogen,  are  readmitted  to  the  still.  The  nickel  i  regenerated 
when  necessary  by  washing  it  with  benzol,  calcining  to  oxide,  converting  into  citrate 
or  formate,  and  reducing  with  hydrogen  at  320  to  350°  C.  Instead  of  providing 
the  cracking-still  with  a  large  exposed  upper  surface,  a  reflux  condenser  may  be  used. 

Planes    Limited  f    produce    saturated    lighter    hydrocarbons    from 
heavier  oil  according  to  the  following  method : 

The  heavier  oil  together  with  nickel  catalyzer  and  hydrogen  or  hydrogen-con- 
taining gas  are  run  into  a  tall  cracking  still,  the  latter  being  provided  with  a  stirring 
device.  As  the  temperature  rises  pressure  is  developed  to  the  desired  point  when  it 
is  relieved  by  a  weighted  valve  into  an  expansion  chamber.  This  chamber  is  fitted 
with  shelves  on  which  are  placed  catalytic  material.  The  vapors  from  the  still 
pass  through  this  chamber  together  with  water  gas  and  are  saturated.  They  are  then 
condensed.  Oil,  catalyzer  and  hydrogen  are  continuously  passed  into  the  still  until 
the  residues  are  too  heavy  to  be  further  cracked,  when  they  are  removed  and  the 
catalyzer  recovered.  The  waste  gases  may  be  returned  to  the  still  provided  they 
are  still  rich  in  hydrogen. 

*  Dec.,  1914,  p.  19. 

t  British  Patent  No.  5,245,  Apr.  1,  1914. 


THE  HYDROGENATICN  OF  PETROLEUM       421 

Mineral  oils  and  residues  are  treated  for  the  production  of  lower  boiling 
hydrocarbons  by  White  *  as  follows: 

The  oil  or  residue,  with  or  without  preliminary  distillation,  is  distributed  in  a 
liquid  state,  and  without  the  addition  of  steam,  on  to  the  surface  of  quicklime  which 
has  been  heated  to  500°  to  600°  C.  in  a  retort  or  chamber.  The  vapors  of  lower 
boiling-point  thus  produced  may  be  drawn  off  by  suction  and  fractionated.  Crude 
paraffin  oil  thus  treated  yields  20  to  25  per  cent  of  hydrocarbons  with  flash-point 
and  boiling-point  similar  to  those  of  gasoline.  The  lime  may  be  regenerated  by 
burning  off  the  deposit  of  carbon,  f 

By  a  process  for  eliminating  sulphur  from  oil,  advanced  by  Evans,  {  the  oil  is 
vaporized,  mixed  with  5  to  10  per  cent  of  hydrogen,  or  with  a  gas  containing  hydro- 
gen, and  passed  over  a  heated  catalytic  or  contact  substance  such  as  nickel  deposited 
on  fire  clay.  Hydrogen  sulphide  is  formed,  and  may  be  removed.  If  the  oil  cannot 
be  distilled,  it  may  be  heated  in  contact  with  the  catalyst  while  hydrogen  is  passed 
through  or  over  it. 

Forges  and  Stransky§  increase  the  volatility  of  hydrocarbons  in  the  following  way : 
the  vapors  of  the  latter,  mixed  with  steam,  at  a  temperature  below  600°,  are  brought 
into  contact  with  metallic  oxides  such  as  the  oxides  of  lead  and  nickel  which  function 
as  catalyzers.  A  portion  of  the  hydrocarbon  is  converted  into  carbon  dioxide  by 
reduction  of  the  metallic  oxide  which  is  regenerated  by  means  of  air  or  oxygen. 

Chichibabin  1 1  suggests  that  the  catalytic  influence  of  metallic  oxides  and  certain 
salts  on  the  formation  of  sulphur  and  nitrogen  containing  substances  and  on  the 
condensation  of  lower  to  higher  hydrocarbons  observed  by  Sabatier  and  by  Ipatiew 
lends  support  to  the  hypothesis  of  the  mineral  origin  of  naphtha,  there  being  an 
abundance  of  such  catalyzers  in  the  bowels  of  the  earth.  As  to  the  optical  activity 
of  natural  naphtha,  it  speaks  neither  for  nor  against  this  hypothesis,  until  its  exact 
causes  are  learned.  To  assume  that  this  activity  is  due  to  living  forces  is  for  the 
present  unwarranted. 

Heyl  and  Baker  Tf  in  their  process  of  producing  motor  spirit,  dissolve 
hydrogen  in  liquid  fuels  such  as  gasoline,  benzine,  or  alcohol  by  spraying 
the  liquid  into  the  gas  within  a  chamber  supplied  with  a  safety  valve. 
The  solution  may  be  passed  over  cold  or  heated  aluminum,  nickel  or  other 
catalyst  in  a  tube  to  aid  the  retention  of  the  gas.  In  a  smaller  apparatus, 
twin  opposing  nozzles  are  used. 

In  the  manufacture  of  condensation  products  from  unsaturated  hydro- 
carbons Sobering  **  uses  anhydrous  inorganic  chlorides,  as  catalyzers. 
These  are  allowed  to  act  upon  mixtures  of  paraffin  hydrocarbons  with 
hydrocarbons  poorer  in  hydrogen  which  contain  at  least  two  double  bonds. 
The  reaction  products  of  a  previous  run  can  be  employed  also  as  catalyzers. 

*  British  Patent  No.  5,434,  Mar.  3,  1914. 
t  J.  S.  C.  I.,  1915,  651. 

t  British  Patent  No.  22,147,  Nov.  6,  1914;   J.  S.  C.  I.,  1915,  1241. 
§  Italian  Patent  No.  142,453,  May  30,  1914;   Chem.  Abs.,  1915,  2814. 
|1  J.  Russ.  Phys.  Chem.  Soc.,  1915,  714;  Chem.  Abs.,  1915,  2489. 
1  British  Patent  No.  11,756,  May  20,  1913. 
**  German  Patent  No.  278,486,  May  24,  1913. 


422  THE  HYDROGENATION  OF  OILS 

Franke  *  claims  that  motor  spirit  is  obtained  from  peat  tar  by  distilling 
up  to  320°  and  redistilling  the  distillate,  preferably  after  it  has  been  puri- 
fied, up  to  250°.  The  second  distillation  may  be  stopped  at  170°,  and  the 
residue  then  heated  up  to  300°  under  pressure  of  25  atmospheres  in  order 
to  crack  it. 

The  cracking  is  accelerated  by  the  addition  of  a  catalytic  agent  capable  of 
recombining  with  the  oil,  the  hydrogen  which  is  evolved  in  the  cracking;  pyro- 
phoric  metals,  such  as  iron,  nickel,  chromium  and  platinum  are  suitable  for  this 
purpose.  The  product  of  the  first  distillation  is  purified  by  treatment  with 
oxidizing  or  condensing  agents,  preceded  by  the  usual  acid  and  alkali  treatment. 
The  oil  is  first  treated  with  sulphuric  acid,  then  washed  and  treated  with  a 
solution  of  caustic  soda  and  again  washed.  Finally  air  is  blown  through  the 
heated  oil  until  it  clarifies.  Instead  of  oxidizing  the  residual  phenolic  compounds 
by  treatment  with  air,  manganese  dioxide  and  sulphuric  acid,  or  peroxides,  per- 
sulphates,  or  chlorates,  may  be  used,  or  condensing  agents  such  as  zinc  or 
aluminum  may  be  employed.  The  resinified  phenolic  compounds  are  removed 
by  filtration  before  the  second  distillation. 

Holcgreber  f  obtains  benzene  by  passing  the  vapors  of  petroleum  or 
its  distillates,  together  with  hydrogen  through  a  tube  containing  catalytic 
materials,  and  heated  to  180  to  300°.  Acetylene  is  said  to  be  first  formed 
and  then  become  polymerized  to  benzene.  Suitable  catalysts  are  iron, 
copper,  zinc,  aluminum,  nickel,  cobalt,  silver  and  platinum  or  mixtures  of 
these  metals. 

Ellis  and  Wells  {  describe  the  results  of  experiments  with  several  forms 
of  tubular  cracking  apparatus  and  the  hydrogenation  of  some  of  the 
products  obtained. 

i 

Using  kerosene  of  42°  B.  (sp.gr.  0.814)  yields  of  gasoline  (boiling-point  up  to  150° 
C.)  of  18  to  20  per  cent  were  obtained  at  450°  to  600°  C.  By  distilling  off  the  gaso- 
line and  retreating  the  residue,  and  also  scrubbing  the  gaseous  reaction  products 
with  oil,  yields  of  40  to  45  per  cent  of  gasoline  were  obtained.  The  gasoline  was 
denser  than  normal  gasoline  of  the  same  boiling-point,  had  a  higher  refractive  index 
and  was  unsaturated;  the  iodine  value  of  the  distillation  fractions  was  higher  the 
lower  the  boiling-point,  a  fraction  boiling  below  70°  C.,  for  example,  having  an 
iodine  value  of  abou  300.  On  standing  for  a  long  time  the  gasoline  became  darker 
in  color,  and  when  subsequently  distilled,  a  violent  reaction  occurred  at  about  160°  C., 
resulting  in  the  production  of  a  dark  brown  viscous  oil.  A  similar  reaction  occurred 
at  about  110°  C.  on  distilling  under  diminished  pressure  (6  to  10  mm.).  The  vis- 
cous polymerized  product  reacted  violently  with  sulphur  and  with  sulphur  chlorides, 
a  viscous  oily  mass  being  produced.  Hydrogenation  improved  the  odor  of  the 
gasoline,  changed  the  color  from  light  straw-color  to  water-white,  and  destroyed 
the  tendency  to  polymerize. 

*  British  Patent  No.  13,361,  June  7,  1913. 
t  British  Patent  No.  17,272,  July  28,  1913. 
J  J.  Ind.  Eng.  Chem.,  1915,  1029;  J.  S.  C.  I.,  1916,  102. 


THE  HYDROGENATION  OF  PETROLEUM       423 

Tinkler  and  Challenger  *  state  that  the  objectionable  smell  of  cracked 
oils  is  removed  by  hydrogenation. 

Danckwardt  f  produces  gasoline  from  crude  oil  by  introducing  a  spray 
of  molten  lead,  alloy  or  fused  sodium  nitrate,  caustic  soda  or  other  liquid, 
insoluble  in  the  oil  and  not  distilling  at  the  temperature  employed,  into  the 
vapor  space  of  the  retort  used  and  thence  into  the  liquid  in  the  retort. 
The  added  material  is  withdrawn  from  the  retort  and  returned  again  to 
the  retort  after  passing  it  through  a  heater.  Vapor  from  the  retort  is 
continuously  drawn  off  and  condensed. 

Testelin  and  Renard  J  have  proposed  an  apparatus  for  rraking  volatile 
hydrocarbons  from  petroleum  in  the  use  of  which  the  oil  is  passed  under 
high  pressure  over  refractory  material  such  as  clay  which  is  maintained  at 
a  red  heat.  Steam  is  introduced  with  the  oil. 

Moeller  and  Woltereck  §  crack  heavy  oils  by  mixing  their  vapors  with 
highly  superheated  steam  at  substantially  atmospheric  pressure  and 
passing  the  mixture  over  coke  at  a  dull  red  heat  (600°  to  800°).  The 
sulphur  present  in  the  oil  is  at  the  same  time  converted  into  hydrogen 
sulphide  and  is  thus  removed  from  the  oil.  The  steam  is  superheated  to 
7CO°  to  800°  in  an  apparatus  which  allows  the  steam  to  expand  while  it 
is  being  heated. 

A  process  for  improving  the  quality  of  hydrocarbon  oils  is  described  by 
the  Badische  Company  ||.  The  oils  are  decolorized  and  deodorized  by 
treatment  in  the  fluid  condition  with  hydrogen,  at  not  above  200°  C., 
at  atmospheric  or  increased  pressure,  and  in  the  presence  of  a  catalyst, 
such  as  nickel,  iron,  cobalt  or  copper,  or  mixtures  of  these. 

The  Badische  Company  ^  produces  hydrocarbons,  which  are  easily  liquefiable, 
and  oxygen  derivatives  of  hydrocarbons  by  passing  carbon  monoxide  and  hydrogen 
mixed  or  not  with  other  gases,  in  the  proportions  of  at  least  two-thirds  of  a  volume 
of  the  former  to  one  volume  of  the  latter,  over  a  heated  catalyst  under  a  high  pressure 
exceeding  that  of  five  atmospheres.  In  examples,  ihe  preparation  of  hydrocarbons 
boiling  from  20°  up  to  250°,  of  olefines,  paraffins,  and  benzine  hydrocarbons,  of 
alcohol,  ketones,  such  as  acetone,  aldehydes  such  as  formaldehyde,  acids  such  as 
acetic  and  its  homologues  and  other  products  are  described.  In  some  cases,  a  basic 
compound  is  added  to  the  catalyst  and  mixtures  of  two  or  more  catalysts  may  be 
employed. 

Brooks,  Bacon,  Padgett  and  Humphrey**  state  that  the  effect  of  pressure 
in  diminishing  the  per  cent  of  olefines  in  the  gasoline  obtained  is  a  note- 

*  Chemistry  of  Petroleum  and  its  Substitutes,  p.  194.     (See  also  pages  243  to  254.) 
f  U.  S.  Patent  No.  1,141,529,  Juno  1,  1915;  Chem.  Abs.,  1915,  1994. 
J  U.  S.  Patent  No.  1,138,  260,  May  4,  1915;  Chem.  Abs.,  1915,  1689. 
§  British  Patent  No.  16,611,  July  19,  1913;   Chem.  Abs.,  1915,  148. 
I!  French  Patent  No.  472,776,  May  28,  1914;  J.  S.  C.  I.,  1915,  540. 
1  British  Patent  No.  20,488,  Sept.  10,  1914. 
**  J.  Ind.  and  Eng.  Chem.,  1915,  180  and  412. 


424  THE  HYDROGENATION  OF  OILS 

worthy  feature  of  their  work.  The  same  effect  is  very  strikingly  shown  in 
the  interesting  results  of  Whitaker  and  Rittman  on  the  effect  of  pressure  in 
the  yield  of  illuminants  in  oil  gas.  At  800°  C.,  Whitaker  and  Rittman 
obtained  from  a  given  quantity  of  oil  122  liters  of  illuminants  at  0.75  Ib. 
pressure,  50  liters  at  atmospheric  pressure  and  15.5  liters  at  45  Ib.  (abso- 
lute) pressure.  They  were  also  able  to  show  that  at  temperatures  of  750°  to 
800°  C.  the  addition  of  hydrogen  to  the  gas  mixture  has  the  effect  of  par- 
tially hydrogenating  the  olefines  and  that  this  reaction  takes  place  more 
readily  as  the  pressure  on  the  system  is  increased.  Ipatiew  *  has  made 
the  interesting  observation  that,  in  the  distillation  of  petroleum  under 
pressure,  at  the  higher  pressure  the  evolved  gases  become  continually 
poorer  in  hydrogen  in  spite  of  the  higher  temperatures  required  to  main- 
tain the  higher  pressures.  The  pressures  employed  by  Ipatiew  were  120 
to  340  atmospheres. 

The  liberation  of  hydrogen  from  petroleum  hydrocarbons  at  variors  temperatures 
has  been  studied  by  Engler  f  and  his  students.  They  obtained  no  hydrogen  below 
470°  at  atmospheric  pressure  from  kerosene  fractions  boiling  below  280°  C.  The 
liberation  of  hydrogen  from  different  hydrocarbons  at  a  given  temperature  depends 
somewhat  on  their  constitution.  Thus,  benzol  yields  appreciable  quantities  of 
hydrogen  only  at  temperatures  above  500°  C. 

The  work  of  Brooks,  Bacon,  Padgett  and  Humphrey  indicates  that  if  hydro- 
genation  of  the  liquid  olefines  takes  place  during  distillation  under  pressure,  it  occurs 
simultaneously  with  their  initial  formation.  A  sample  of  cracked  naphtha,  having 
an  iodine  number  of  55.0  was  heated  to  196°  C.  with  hydrogen  for  thirty  hours  under 
3000  Ib.  pressure  per  square  inch.  The  iodine  number  and  refining  loss  with  sul- 
phuric acid  were  practically  unaffected,  the  iodine  number  of  the  final  product  being 
52.9.  Results  closely  parallel  to  this  were  obtained  by  Rhodes,  working  with  liquid 
fatty  oils.  The  apparatus  employed  was  a  steel  bomb  connected  with  a  solenoid 
stirrer  constructed  as  described  by  Stucker  and  Enduli.  J  Uebbelohde  and  Woronin  § 
showed  that  in  the  presence  of  nickel,  hydrogen  was  split  off  from  a  Baku  crude  oil 
at  as  low  a  temperature  as  180°  C.  The  results  of  Zelinski  ||  with  dehydrogenation 
at  temperatures  above  300°  C.  in  the  presence  of  platinum  is  to  be  expected.  Ostro- 
misslenski.and  Bujanadse  If  showed  that  in  the  presence  of  nickel  a  Russian  crude 
oil  gave  only  coke,  40  per  cent,  and  gas  at  temperatures  between  660°  to  700°  C., 
no  tar  or  liquid  being  obtained  at  all.  Furthermore,  the  gas  contained  72  to  75  per 
cent  of  hydrogen  and  the  remainder  consisted  of  saturated  hyrdocarbons.  These 
facts  are  quite  significant  in  view  of  the  proposed  cracking  processes  of  Vernon  Boys, 
Lamplough  and  others,  who  introduce  nickel  into  the  cracking  zone.  A  series  of 
experiments  were  made  by  Brooks,  Bacon  Padgett  and  Humphrey  at  atmospheric 
pressure  and  at  temperatures  of  500°  to  550°  C.,  employing  various  catalytic  sub- 
stances. Kerosene  and  solar  oil  vapors  passed  through  an  iron  tube  containing 

*  Ber.,  1904,  2969. 

f  Engler  and  Hofer,  Das  Erdol,  1,  574. 

JZei  schr.  f.  Elektroch.,  1913,  570. 

§  Petroleum,  Berlin,  1911,  7. 

||  Ber.,  1912,  45,  3678. 

t  J.  Russ.  phys.-chem.  Ges.,  1910,  195. 


THE  HYDROGENATION  OF  PETROLEUM  425 

burned  clay,  carbon,  coarse  and  finely-divided  iron,  coarse  and  finely-divided  copper, 
heated  to  the  above-named  temperature,  yielded  gasoline  fractions,  which  showed 
an  olefine  content  of  approximately  25  to  3Q  per  cent.  When  nickel  was  employed 
the  per  cent  of  defines  in  the  gasoline  product  was  48  per  cent. 

Humphreys  *  obtains  low  boiling  hydrocarbons  from  liquid  paraffin 
hydrocarbons  of  petroleum  which  boil  at  260°  or  higher  by  distilling  a 
portion  of  the  liquid  under  four  atmospheres  or  higher  pressure  at  a 
temperature  of  340°  to  455°  in  a  still  containing  steel,  brass  or  copper 
plates  immersed  in  the  liquid.  The  plates  are  stated  to  have  a  catalytic 
action  in  forming  lighter  hydrocarbons  and  about  65  to  70  per  cent  of  the 
liquid  treated  is  distilled  off  and  condensed. 

A  process  and  apparatus  for  converting  heavy  into  light  hydro- 
carbons is  described  by  Porges,  Stfansky  aT:d  Strache.f 

A  mixture  of  the  vaporized  oil  a::d  steam  is  passed  over  a  catalyst 
(iron  oxide  or  oxide  of  another  metal  capable  cf  forming  several 
cxides),  which  is  heated  to  500  to  600°  C.,  and  light  products  are 
formed.  When  the  hydrocarbons  begin  to  diminish  the  catalyst  is 
regenerated  by  heating  it  in  a  current  of  air  or  oxygen. 

The  Continental  Caoutchouc  and  Gutta  Percha  Co.{  heat  a  mineral  oil 
fraction  of  high  boiling-point  with  a  catalyst  such  as  aluminum  chloride, 
with  or  without  mercuric,  ferric,  vanadium,  or  other  chloride,  or  with 
aluminum  in  a  stream  of  dry  hydrochloric  acid  gas,  or  the  oil  is  atomized 
and  exposed  to  ultra  violet  rays  or  the  silent  electric  discharge  in  presence 
of  a  catalyst.  The  process  is  continuous.  Gaseous  products  are  obtained 
by  heating  to  a  higher  temperature,  and  longer,  in  closed  vessels.  § 

Brooks |!  obtained  from  3  to  20  per  cent  of  gasoline,  boiling  below  150°  C., 
by  cracking  Texas  solar  oil  (sp.  gr.  0.8862)  alone  and  in  the  presence  of 
various  contact  substances,  at  temperatures  between  400°  and  600°  C., 
at  atmospheric  pressure;  the  gasoline  was  highly  unsaturated,  the  loss 
by  treatment  with  concentrated  sulphuric  acid  averaging  about  28  per  cent. 
Various  proposed  methods  of  hydrogenation  are  also  considered;  the  oil- 
steam  iron  process  for  hydrogenating  olefmes  and  preventing  deposition 
of  carbon  is  stated  t"o  be  inadequate. 

The  disagreeable  odor  of  highly  cracked  gasoline  was  removed  by  treatment 
(desulphurization)  with  alkaline  plumbite,  copper  oxide,  or  metallic  sodium.  In 
experiments  on  the  distillation  of  heavy  petroleum  oils,  mainly  Oklahoma  reduced 
oil,  30°  B.  (sp.gr.  0.875)  under  pressures  up  to  450  Ib.  per  square  inch,  the  yield  of 

*  U.  S.  Patent  No.  1,122,003,  Dec.  22,  1915;  Chem.  Abs.,  1915,  374. 
t  British  Patent  No.  11,420,  May  8,  1914.     See  also  U.  S.  Patent  1,205,578,  Nov.  21, 
1916,  to  Strache  and  Porges. 

J  French  Patent  No.  469,948,  March  21,  1914. 

§  Chem.  Abs.,  1915,  19. 

II  J.  Franklin  Inst.,  1915,  180,  653;  J.  S.  C.  I.,  1916,  102. 


426  THE  HYDROGENATION  OF  OILS 

gasoline  increased  with  the  pressure,  up  to  about  32  per  cent  at  250  lb.,  and  then 
declined;  the  olefine  content  of  the  gasoline  decreased  as  the  pressure  increased  up 
to  200  lb.  and  then  remained  constant,-  this  result  being  ascribed  to  polymerization 
rather  than  hydrogenation.  As  regards  processes  in  which  oil  is  cracked  while  in 
the  form  of  vapor,  it  is  pointed  out  that  heavy  oil  can  only  be  completely  vaporized 
at  very  low  pressures.  Gasoline  obtained  by  cracking  the  vapor  of  Oklahoma 
reduced  oil  under  a  pressure  of  100  lb.  per  square  inch,  consisted  chiefly  of  normal 
paraffin  hydrocarbons  but  contained  about  8  per  cent  of  benzene,  toluene,  and 
ra-xylene.  The  formation  of  aromatic  hydrocarbons  rom  petroleum  oils  by  this 
means  is  regarded  as  due  to  the  splitting  or  cracking  of  high-boiling  complex  hydro- 
carbons containing  the  phenyl  radicle  (not  to  the  dehydrogenation  of  naphthalenes, 
formation  of  acetylene,  and  condensation  of  the  latter  to  benzene,  etc.),  and  evidence 
is  adduced  in  support  of  this  hypothesis. 

The  Scientific  American,*  observes  that  an  English  company  is  securing  a  very 
large  yield  of  gasoline  from  petroleum  by  catalytic  hydrogenation.  The  method 
is  practically  the  same  as  that  recently  applied  in  the  conversion  of  liquid  fats  to  a 
solid  form  or  to  solid  fatty  acids  with  a  higher  value.  A  tall  still  with  a  conical  bot- 
tom receives  a  steady  feed  of  petroleum  and  hydrogen  gas  under  pressure.  This 
mixture  enters  at  the  bottom  and  passes  over  finely-divided  nickel  which  catalytically 
brings  about  a  reaction  between  the  hydrogen  and  oil.  Gasoline  is  formed  which 
passes  off  as  a  vapor  at  the  temperature  of  the  still,  while  the  heavier  hydrocarbons 
formed  fall  back  into  the  catalyst  and  react  with  hydrogen.  Finally  a  tarry  residue 
must  be  removed  and  the  nickel  regenerated.  The  issuing  gases  pass  into  a  cooling 
chamber  where  the  gasoline  is  condensed.  The  hydrogen  unused  up  to  that  point  is 
forced  back  and  passed  through  the  still  once  more. 

By  a  cracking  process  of  Valpy  and  Lucas,  |  steam  is  superheated  to  a 
temperature  slightly  below  the  cracking-point  and  is  sprayed  into  the  oil 
in  a  still.  The  mixture  of  oil,  vapor  and  steam  is  passed  through  heated 
catalyzing  tubes  of  nickel,  which  may  be  packed  with  catalyzing  material, 
and  thence  to  a  coil  in  the  oil  still  where  the  heat  of  the  cracked  vapor  is 
utilized  for  heating  the  oil.  The  catalyzing  tubes  may  be  heated  elec- 
trically, or  by  an  oil  burner.  J 

A  modification  of  this  method  of  cracking  oil  of  Valpy  and  Lucas,  § 
consists  in  removing  oil  vapor  from  a  still  by  means  of  steam  or  an  inert 
gas  under  pressure  and  the  mixture  is  brought  into  contact  with  a  heated 
catalyst,  such  as  nickel  or  one  of  its  alloys,  or  nickel  *suboxide  or  oxide, 
and  the  pressure  of  the  mixture  after  leaving  the  catalyzing  chamber  is 
reduced  suddenly.  The  light  oils  produced  are  condensed.  || 

A  catalyst  for  cracking  petroleum  oils  described  by  Lucas  If  is  prepared 
by  heating  a  mixture  of  oxides  and  oxalates  of  iron  and  nickel,  chromium 

*  May  23,  1914,  p.  425. 

t  British  Patents  Nos.  20,470,  Sept.  10,  1913  and  2838,  Feb.  3,  1914. 

J  J.  S.  C.  I.,  1915,  71. 

§  British  Patents  Nos.  12,653,  May  22,  and  18,923,  Aug.  21,  1914. 

||  J.  S.  C.  I.,  1915,  707. 

1  U.  S.  Patent  No.  1,168,404,  Jan.  18,  1916. 


THE  HYDROGENATION  OF  PETROLEUM  427 

or  cobalt  to  a  sintering;  temporal  uro  with  small  amounts  of  carbon  and 
aluminum,  magnesium  or  cerium  to  reduce  the  metallic  compounds.  The 
metallic  catalyst  thus  formed  retains  its  efficiency  in  continued  use  for 
cracking  oils  for  a  considerable  time. 

For  the  production  of  light  hydrocarbons  from  heavier  oils  and  the  like, 
Sabatier  and  Mailhe  *  recommend  a  two-stage  method  as  follows: 

First  stage:  The  vapors  coming  from  solid  or  liquid  hydrocarbons  to  be  treated 
are  directed  against  wires  or  metal  blades  rendered  incandescent  by  an  electric 
current.  The  liquid  to  be  converted,  or  its  vapor,  is  brought  into  contact  with  them 
either  alone  or  mixed  with  hydrogen  or  any  gas  rich  in  hydrogen.  Wires  of  various 
metals  can  be  employed,  either  platinum  or  metal  of  the  platinum  series,  iron,  cop- 
per, cobalt,  tantalum  or  any  wires  that  can  be  rendered  incandescent  by  an  electric 
current  of  any  kind,  or  wires  covered  with  catalyzing  metals  or  oxides,  such  as 
oxides  of  thorium,  zirconium,  uranium,  titanic  acid  or  mixtures  of  these  oxides. 
The  temperature  of  the  wires  is  raised  by  the  passage  of  electric  current  from  300° 
to  dark  or  bright  red.  The  dissociation  of  hydrocarbon  products  into  more  volatile 
hydrocarbon  products  is  the  more  complete,  the  greater  the  length  of  contact  of  the 
wires,  or  the  surface  of  the  catalyzing  metals,  or  catalyzing  oxides  heated  by  wires 
through  which  an  electric  current  is  passing.  The  output  of  volatile  liquid  products 
and  of  gas  is  the  greater,  the  higher  the  temperature.  At  the  outlet  of  the  apparatus 
in  which  the  kerosene  or  heavy  petroleum  oils,  have  been  exposed  to  the  catalytic 
action,  condensing  apparatus  is  provided  to  cool  the  products  of  the  reaction  which 
comprise:  1.  Hydrocarbon  gases  mixed  with  hydrogen,  which  can  be  utilized  either 
directly  for  heating  and  lighting,  or  for  explosion  engines,  or  as  compressed  gases  for 
lighting  or  for  the  manufacture  of  hydrogen  by  destructive  distillation.  2.  Liquid 
hydrocarbons  distilling  below  150°,  containing  non-saturated  oxidizable  hydrocar- 
bons which  are  treated  in  the  second  stage.  3.  Liquid  hydrocarbons  distilling 
between  150°  and  300°,  which  can  either  be  mixed  again  with  the  original  raw  mate- 
rial, in  order  to  be  submitted  to  a  new  treatment,  or  submitted  to  the  action  of  the 
second  stage  in  order  to  render  them  suitable  for  lighting  purposes.  4.  Liquid  or 
solid  products  which  do  not  distil  under  300°,  and  which  must  be  mixed  again  with 
the  original  raw  material,  in  order  to  be  submitted  to  a  new  treatment.  5.  Solid 
carbon  substances  which  are  separated. 

Second  stage:  The  liquids  which  are  volatile  under  150°,  as  well  as  those  which 
distil  between  150°  and  300°,  are  constituted  for  the  greater  part  of  non-saturated 
oxidizable  hydrocarbons,  which  can  be  utilized  immediately  for  explosion  engines, 
lighting,  etc.,  or  converted  into  saturated  hydrocarbons  which  are  practically  non- 
oxidizable  in  the  air,  by  direct  hydrogenation  of  their  vapors  by  means  of  divided 
nickel  or  similar  metals.  In  order  to  carry  out  this  second  stage,  hydrogenation 
may  be  effected  by  using,  in  place  of  divided  nickel  or  similar  metals,  a  nickel  wire, 
blade  or  tube  arranged  in  the  form  of  a  spiral  or  net  work,  heated  to  a  temperature 
between  200°  and  350°  by  the  passage  of  an  electric  current.  Cobalt,  copper,  iron, 
platinum,  or  metals  of  the  platinum  series  may  be  similarly  employed.  Divided 
nickel,  copper,  cobalt,  iron,  obtained  by  the  reduction  of  their  oxides;  platinum  in 
its  various  forms,  or  metals  of  the  platinum  group,  supported  on  a  metallic  conductor 
also  are  recommended. 

*U.  S.  Patent  No.  1,124,333,  Jan.  12,  1915;  Chem.  Abs.,  1915,  710.  French  Patent 
No.  475,303,  Feb.  4,  1914;  J.  S.  C.  I.,  1916,  34. 


428  THE  HYDROGENATION  OF  OILS 

Sabatier  and  Mailhe,*  in  their  process  of  cracking  oils  by  passing  oil 
vapors  over  a  catalyst  at  temperatures  between  400°  and  dark  red  heat, 
prepare  the  catalyst  of  finely-divided  metal  or  metals,  or  metallic  oxides 
or  salts  that  can  be  reduced  to  form  divided  metal,  together  with  neutral 
refractory  substances  free  from  silica  and  an  agglutinant  free  from  silica. 

Suitable  refractory  materials  are  magnesia,  alumina,  bauxite,  lime,  baryta, 
strontia,  or  the  corresponding  carbonate,  or  graphite.  Suitable  agglutinants  are 
glue,  dextrin  and  starch.  Examples  of  such  compounds  comprise:  (1)  iron  filings, 
magnesium  oxide  and  dextrin;  (2)  oxide  of  iron,  magnesium,  bauxite  and  glue; 
(3)  finely-divided  iron,  alumina  and  dextrin.  The  resulting  compounds  are  moulded 
and  dried  and  packed  into  cracking  tubes  composed  of  metal  or  earthenware  lined 
with  a  non-siliceous  coating.  When  the  catalyst  loses  its  activity  by  reason  of  the 
deposition  of  carbon,  it  is  revivified  by  the  passage  of  steam,  a  gaseous  mixture  of 
hydrogen,  carbon  monoxide  and  carbon  dioxide  being  produced.  This  gas  can  be 
utilized  as  a  reducing  agent  or  fuel,  the  carbon  dioxide  being  removed  by  washing  if 
necessary.  The  metallic  oxide  formed  by  the  steam,  and  the  oxide  used  in  making 
the  catalyst  initially,  are  reduced  to  metal  by  means  of  hydrocarbon  vapors.  The 
volatile  portion  of  the  products  of  the  cracking  operation,  namely,  that  distilling 
below  150°,  is  treated  for  the  removal  of  the  malodorous  unsaturated  compounds 
by  reduction  with  hydrogen  in  the  presence  of  finely-divided  metals  at  150°  to  300°. 

/     Hall  f  cracks  oils  for  the  manufacture  of  motor  spirit  by  heating  the 

/     vapors  of  the  heavy  hydrocarbons  under  pressure  in  the  presence  of  a 

\     catalyst  capable  of  affixing  hydrogen  to  hydrocarbons,  then  allowing  the 

\    vapors  to  expand  and  deposit  carbon,  and  finally  condensing  the  vapors 

with  or  without  preliminary  dephlegmation  or  subsequent  distillation. 

The  operation  may  be  conducted  under  a  pressure  of  five  atmospheres  and  at  a  tem- 
perature of  600°  and  upwards.  Gas  oil  treated  in  this  way  yields  50  to  70  per  cent 
of  oil  of  sp.gr.  0.765  suitable  for  gasoline  engines.  Metals  such  as  nickel,  cobalt, 
silver,  palladium,  chromium  or  manganese,  or  their  oxides,  may  be  used  as  catalysts. 
In  one  form  of  apparatus  the  oil  passes  through  a  preheater  into  a  converter  consist- 
ing of  tubes  containing  cylindrical  nickel  rods,  and  the  products  escape  through  a 
reducing-valve  into  an  expansion  chamber,  fitted  with  a  metallic  gauze  screen  and 
thence  to  a  condenser. 

The  unsaturated  materials  formed  during  the  process  are  claimed  to  be  saturated 
with  hydrogen  which  is  derived  from  the  oil  itself.  No  water,  steam,  hydrogen  or 
outside  source  of  hydrogen  is  used.  { 

In  a  paper  by  Hall  on  the  cracking  of  oils  read  before  "  The  Institution 
of  Petroleum  Technologists/'  1914,  the  utility  of  steam  as  a  source  of 
hydrogen  in  cracking  processes  involving  passing  oil  through  heated  tubes, 
is  discussed  by  Hall,  who  states: 

*  British  Patent  No.  16,791,  July  14,  1914;  Chem.  Abs.,  1916,  273;  U.  S.  Patent  No. 
1,152,765;  Chem.  Abs.,  1915,  2814. 

t  British  Patent  No.  17,121,  July  25,  1913;  J.  S.  C.  I.,  1914,  1149.  See  also  U.  S. 
Patent  No.  1,261,930,  April  9,  1918;  Chem.  Abs.,  1918,  1597. 

J  U.  S.  Patent  No.  1,175,909,  March  14,  1916. 


THE  HYDROGENATION  OF  PETROLEUM       429 

"As  far  as  any  advantage  from  the  use  of  water  as  a  hydrogenating  agent  is 
concerned,  I  am  sure  it  is  nil,  whether  with  or  without  a  catalytic  combiner,  and 
I  have  operated  fair-sized  apparatus  for  weeks  with  nickel  and  other  so-called  cata- 
lyzers, first  with  and  then  without  water,  and  we  could  never  notice  any  material 
difference.  If  hydrogen  without  oxygen  is  utilized,  better  results  are  obtained,  but 
the  expense  appeals  to  be  prohibitive.  With  nickel  rods  in  the  tubes,  and  with 
water  used  with  the  oil,  I  have  found  the  rods  so  heavily  coated  after  a  six-  or  eight- 
hour  run,  that  the  coating  could  only  be  removed  by  buffing.  It  was  impossible 
in  any  way  to  wipe  it  off.  The  substitution  of  copper  for  nickel  rods  gave  equally 
good  results.  In  large  tubes,  1  in.  or  more,  water  in  excess  of  8  per  cent  or  10  per 
cent  is  utterly  impracticable,  if  the  process  is  conducted  under  pressure,  and  at  any 
rate  of  feed  that  would  be  commercially  economical,  as  no  uniform  pressures  can  be 
maintained." 

Hall  further  states  that  *  the  admixture  of  water  or  steam  with  the  oil 
during  cracking  neither  prevents  decomposition  of  carbon  nor  promotes 
hydrogenation  of  the  unsaturated  hydrocarbons.  The  latter,  in  large 
proportion,  are  objectionable  in  cracked  spirit  mainly  because  of  the 
resinous  carbon  colloid  with  which  they  are  usually  associated  and  which, 
by  oxidation,  tends  to  form  a  varnish-like  product  detrimental  to  the  work- 
ing of  motor  engines.  Owing  to  the  combination  effected  in  the  com- 
pressor between  the  condensable  vapor  and  the  fixed  gases,  the  spirit 
obtained  by  HalPs  method  is  stated  to  be  largely  free  from  this  objection. 

By  another  modification  of  the  Hall  process  f  motor  spirit  is  produced  by  passing 
a  kerosene  fraction  boiling  up  to  about  220°,  from  which  the  gasoline  has  been 
removed,  between  minute  interstices  under  very  high  pressure,  such  as  1000  to  3000 
Ib.  per  square  inch,  in  the  presence  of  hydrogen,  coal  gas,  or  other  gas  containing 
free  hydrogen  or  a  hydrocarbon  gas  such  as  ethylene  or  oil  gas,  and  at  a  temperature 
not  above  the  lowest  boiling-point  of  the  liquid,  e.g.,  100°  to  120°.  Combination 
of  the  gas  and  oil  is  said  to  take  place.  Suitable  apparatus  comprises  a  series  of 
discs  or  plugs,  preferably  nickel  between  or  through  which  the  liquid  is  forced.  The 
discs  or  plugs  may  be  scratched  to  form  fine  grooves.  J 

Lamplough  §  comments  on  the  relative  value  of  various  catalysts  em- 
ployed in  bringing  about  reaction  between  the  vapors  of  oils  and  water. 

He  states  that  burnt  clay  or  aluminum  silicate,  which  has  frequently  been  rec- 
ommended, is  very  slow  in  action  and  is  open  to  the  objection  that  the  clay  is  apt  to 
become  clogged  by  deposition  of  tarry  masses  which  can  be  removed  only  with  great 
difficulty.  The  use  of  iron  as  a  catalyzer  is  stated  to  be  open  to  the  objection  that 
if  the  water  vapor  is  used  in  excess  the  iron  will  rust  and  become  unsuitable  for 
use.  Nickel  in  the  form  of  fine  particles  is  similar  to  clay  with  respect  to  becoming 
coated  with  particles  of  tarry  or  carbonaceous  matter.  On  the  other  hand  nickel 
in  the  form  of  a  compact  metal  has  been  found  by  test  to  remain  free  of  carbon 
deposits,  while  exhibiting  the  desired  catalytic  effect. 

*  J.  Inst.  Petrol.  Techn.,  1915,  1,  147;  J.  S.  C.  I.,  1916,  296. 

t  British  Patent  No.  103,720,  Mar.  4,  1916;  Chem.  Abs.,  1917,  2043. 

j  See  French  Patent  No.  481,066,  Feb.  25,  1916. 

§  U.  S.  Patent  No.  1,229,098,  June  5,  1917. 


430  THE  HYDROGENATION  OF  OILS 

A  fuel  suitable  for  use  in  automobile  engines  is  obtained  by  Higgins  and  Preston  * 
from  heavy  hyd~ocarbon  oils  by  heating  them  in  a  converter  under  pressure  to  a 
temperature  sufficient  to  volatilize  the  heaviest  constituent  of  the  oil,  passing  the 
vapors  alone  or  with  hydrogen  gas  over  a  catalyst,  and  condensing  them  in  contact 
with  the  catalyst.  The  apparatus  comprises  a  converter  fitted  with  a  pressure- 
regulating  valve  which  is  kept  closed  until  the  requisite  temperature  is  reached. 
After  the  valve  is  opened,  the  vapors,  together  with  hydrogen  admitted  into  the 
converter,  pass  to  a  condenser  which  contains  a  cartridge  of  catalyst.  The  catalyst 
may  consist  of  nickel  oxide  and  pumice  stone.  The  process  may  be  applied  to  the 
treatment  of  shale  oil,  crude  benzene,  crude  naphtha,  crude  tar  oil,  or  paraffin  oil, 
or  to  mixtures  of  crude  benzene  with  crude  naphtha,  paraffin  oil,  or  coal-tar  oil. 

A'  process  of  making  gasoline  from  heavier  oils  by  cracking  is  described 
by  Low.  f 

In  one  form  of  this  process  the  oil  to  be  cracked  is  sprayed  into  contact  with  a 
heating  element  which  may  carry  a  catalytic  body.  Iron,  nickel,  cobalt  and  copper 
are  mentioned  for  this  purpose.  The  spraying  operation  may  be  carried  out  in  a 
closed  vessel  in  an  atmosphere  of  hydrogen  or  blue  water  gas.  Under  such  condi- 
tions it  is  stated  that  unsaturated  compounds  may  be  converted  into  saturated  com- 
pounds. A  hot  nickel  surface  in  a  hydrogen-containing  atmosphere  is  particularly 
advantageous  in  causing  the  formation  of  saturated  gasoline  from  heavy  oils  pro- 
jected against  such  surface. 

According  to  a  process  devised  by  Wells  J  directed  to  the  production  of 
gasoline  from  heavier  petroleum  products,  oil  vapors  are  conducted  into  a 
bath  of  molten  lead,  which  is  heated  to  about  480°  to  540°  C.  and  violently 
agitated  by  mechanical  means  at  the  moment  of  contact.  § 

Wells  1 1  also  recommends  the  following  cracking  process:  Preheated 
kerosene  or  a  heavier  petroleum  oil  is  fed  through  a  hot  cracking  chamber 
filled  with  jackstones  coated  with  nickel  or  other  catalyst  and  the  crude 
gasoline  thus  formed  is  preferably  refined  by  a  further  treatment  with 
hydrogen  and  a  catalyst  at  a  temperature  of  about  240°. 

•>/     In  cracking  petroleum  oils  in  the  presence  of  hydrogen,  Whitaker  and 

/  Xeslie  ]f  have  reached  the  following  conclusions : 

1.  That  effects  often  ascribed  to  catalysis  are  in  reality  due  to  effective 
heat  transfer  by  conduction  and  convection  from  the  large  heated  sur- 
faces exposed  to  the  gases. 

2.  That  hydrogen  is  produced  from  an  oil  even  when  the  cracking  takes 
place  in  hydrogen. 

3.  That  considerable  absorption  of  hydrogen  takes  place  when  an  oil  is 
cracked  in  an  atmosphere  of  hydrogen,  and  this  absorption  is  greater  the 

*  British  Patent  No.  23,876,  Dec.  10,  1914;   Chem.  Abs.,  1916,  1594. 

t  U.  S.  Patent  No.  1,192,653,  July  25,  1916. 

J  U.  S.  Patent  No.  1,187,874,  June  20,  1916. 

§  J.  S.  C.  I.,  1916,  883. 

||  U.  S.  Patent  No.  1,248,225,  Nov.  27,  1917. 

If  J.  Ind.  Eng.  Chem.,  1916,  694. 


THE  HYDROGENATION  OF  PETROLEUM  431 

higher  the  concentration  of  hydrogen,  the  higher  the  temperature  (within 
the  range  studied),  and  the  lower  the  oil  rate. 

4.  That  no  marked  and  consistent  difference  in  the  amount  of  tar  formed 
when  an  oil  is  decomposed  alone  or  in  hydrogen  at  temperatures  of  723°  C. 
or  below  is  noticeable.     At  825°  C.  less  tar  is  formed  when  the  oil  is  cracked 
in  hydrogen.     The  tars  formed  below  723°  C.  are  in  large  part  unchanged 
or  partly  changed  oil,  whereas  those  tars  formed  above  800°  C.  are  essen- 
tially composed  of  synthetic  products. 

5.  That  the  reactions  which  result  in  decreasing  the  proportion  of 
illuminants  are  the  most  rapid. 

6.  That  the  presence  of  hydrogen  during  the  decomposition  of  an  oil 
has  the  effect  of  increasing  largely  the  proportion  of  the  carbon  of  the  oil 
appearing  as  hydrocarbons  in  the  gas. 

7.  That  with  correct  design  of  apparatus,  and  proper  adjustment  of 
temperature,  rate  of  oil  feed,  and  concentration  of  hydrogen  it  is  possible 
to  obtain  gases  of  widely  varying  compositions. 

A  method  of  cracking  heavy  hydrocarbons  in  the  presence  of  hydrogen, 
proposed  by  Bergius*  involves  treatment  in  an  autoclave  at  a  temperature 
below  500°  and  under  a  pressure  of  over  20  atmospheres  in  order  to  obtain 
light  hydrocarbons  in  the  form  of  saturated  benzine,  f  As  an  example. 
11  kilos,  of  gas  tar  are  heated  with  hydrogen  at  100  atmospheres  pressure, 
to  400°  C.  After  four  hours  the  mass  is  distilled  at  about  250°  C.,  and 
about  60  per  cent  of  distillate  resembling  petroleum  oil  is  obtained,  which 
can  be  further  treated  by  rectification.  J 

A  A  most  interesting  and  ingenious  method  of  hydrogenating  coal  is 
described  by  Bergius  and  Billwiller.§  These  investigators  find  on  heating 
coal  with  hydrogen  to  a  temperature  between  300°  and  500°  C.,  involving 
pressures  up  to  200  atmospheres,  the  hydrogen  combines  with  the  coal, 
forming  hydrocarbons  which  are  liquid  at  ordinary  temperature  or  have  a 
low  melting-point.  Only  a  very  small  amount  of  methane  is  produced. 
Thus,  they  obtain  distillates  from  coal  amounting  to  nearly  100  per  cent 
of  the  carbonaceous  substance,  whereas  by  the  usual  method  of  distilling 
coal  the  liquid  products  usually  do  not  exceed  3  per  cent.  The  nitrogen 
contained  in  the  coal  is  transformed  into  ammonia.  Some  bodies  of  the 
phenolic  type  are  produced.  The  reaction  is  shortened  if  a  solvent  such 
as  benzene  is  employed.  The  process  is  applicable  to  the  treatment  of 

*  Austrian  Patent  No.  71,208,  June  26,  1916;  French  Patent  No.  470,551,  Apr.  6,  1914; 
J.  S.  C.  I.,  1915,  167. 

t  British  Patent  No.  5,021,  Mar.  31,  1915.  Addition  to  18,232  of  1914;  J.  S.  C.  I., 
1916,  167,  732. 

t  J.  S.  C.  I.,  1915,  862. 

§U.  S.  Patent  No.  1,251,954,  Jan.  1,  1918. 


432  THE  HYDROGENATION  OF  OILS 

wood,  peat,  tar  and  pitch  in  like  manner.  Bergius  and  Billwiller  give 
several  illustrations  of  the  method  of  procedure,  the  following  being  noted : 
1.  400  kg.  powdered  coal  are  filled  into  a  pressure-resisting  vessel  of 
about  400  liters  capacity,  which  is  connected  to  a  tank  in  which  hydrogen 
is  held  under  200  atmospheres  pressure.  After  fifteen  hours  the  con- 
nection with  the  hydrogen  tank  is  turned  off  and  the  vessel  is  emptied. 
About  10  to  15  kg.  of  hydrogen  have  then  been  consumed,  according  to  the 
quality  of  coal  used.  From  the  contents  of  the  vessel  more  than  half  of 
the  coal  can  be  separated  from  solid  residue  as  liquid.  The  remaining 
part  of  liquid  products  in  the  solid  residue  can  be  gained  by  extraction. 

2.  150  kg.  powdered  coal  are  placed  with  an  equal  quantity  of  heavy  ben- 
zine in  a  pressure-resisting  vessel  of  about  400  liters  capacity,  connected 
to  a  hydrogen  tank.  For  the  purpose  of  mixing,  the  vessel  is  rotated. 
After  twelve  hours,  at  a  temperature  of  400°,  the  vessel  is  opened  and  the 
liquid  produced  is  separated  from  the  solid  residue.  Only  15  per  cent  of 
the  weight  of  coal  employed  is  then  left.  The  remaining  85  per  cent  is 
dissolved  in  the  benzene.  The  consumption  of  hydrogen  is  about 
5kg. 

One  modification  of  a  method  of  cracking  oils  used  by  Ellis  *  involves 
passage  of  the  raw  oil  material,  such  as  kerosene,  through  a  heated  zone 
containing  catalytic  bodies,  in  the  presence  of  added  gases  derived  from 
the  decomposition  of  oil  which  has  previously  passed  through  the  cracking 
zone.  In  another  modification  f  kerosene  or  other  oils  heavier  than  gas- 
oline are  decomposed  by  heating  in  a  series  of  superposed  nearly  hori- 
zontal pipes.  The  temperature  of  the  oil  is  gradually  increased  as  it 
passes  through  the  pipes  and  after  the  maximum  cracking  temperature 
desired  has  been  attained  the  heating  is  continued  in  the  presence  of 
catalytic  material  at  a  gradually  decreasing  temperature,  until  the  products 
have  assumed  a  state  of  stable  equilibrium.  The  gasoline  is  then 
condensed. 

An  apparatus  described  by  the  Standard  Oil  Co.J  for  converting  heavy 
hydrocarbons  into  gasoline  and  other  light  oils  §  consists  of  a  still  con- 
taining catalytic  plates  suspended  in  the  vapor  space,  or  interlocking  down- 
wardly convex  plates  supported  by  hinges  and  extending  over  the  bottom 
of  the  still  in  such  a  manner  as  to  provide  for  the  circulation  of  the  oil. 
The  catalytic  surfaces  may  consist  of  copper,  brass,  steel,  or  other  metal  in 
the  form  of  solid  plates  or  gauze  plates;  plates  of  mineral  fibres  such  as 
asbestos  or  glass  may  also  be  used. 

*  U.  S.  Patent  No.  1,216,971,  Feb.  20,  1917. 

t  U.  S.  Patent  No.  1,249,278,  Dec.  4,  1917. 

j  British  Patent  No.  7,541,  Oct.  20,  1914;   Chem.  Abs.,  1916,  2798. 

§  Using  the  process  described  in  British  Patent  No.  29,862,  1912;   Chem.  Abs.,  8,  2058. 


THE  HYDROGENATION  OF  PETROLEUM 


433 


The  use  of  sulphur  to  promote  the  cracking  of  heavier  oils  to  yield 
lighter  products  such  as  naphtha  or  benzine  is  suggested  by  Day.* 

He  states  that  by  adding  sulphur  or  a  sulphur  compound  to  crude  oils  or  distillates 
containing  little  or  no  sulphur  such  oils  can  be  more  easily  decomposed  by  heat  under 
the  proper  pressure  with  the  production  of  an  increased  yield  of  distillates  lighter 
in  specific  gravity  than  those  which  would  be  produced  by  the  ordinary  process  of 
simple  distillation.  It  is  also  stated  that  the  distilling  operation  may  be  carried 
out  in  the  presence  of  a  hydrogen-containing  gas  and  a  catalytic  agent  or  porous 
contact  substance  in  the  manner  previously  proposed  by  Day  (see  pages  10  and  20). 
The  sulphur  may  be  added  to  the  oil  in  the  form  of  the  sulphide  of  ammonium, 
sodium,  iron  or  copper  or  as  hydrogen  sulphide.  Sulphates  are  not  applicable  for 
use  in  this  process.  A  perforated  supply  pipe,  see  Fig.  56c,  for  admitting  oil  and  gas 


n 


tr 


FIG.  56c. 

is  placed  near  the  bottom  of  the  still.  Hydrogen  and  hydrogen  sulphide  may  be 
admitted  at  this  point.  Contact  material  in  the  tubes  above  the  perforated  pipe 
may  be  iron  by  hydrogen,  zinc  dust,  reduced  nickel  or  cobalt,  dry  porous  clays, 
spongy  platinum,  or  palladium.  Day  states  he  has  found  that  the  cracking  opera- 
tion is  greatly  aided  by  passing  a  hydrogen-carrying  gas  or  vapor,  such  as  hydrogen 
sulphide,  ammonia,  illuminating  gas,  or  water  gas,  or  steam  through  the  oil  and 
thence  passing  the  commingled  oil  vapors  and  hydrogen  from  the  space  above  the 
oil  through  porous  absorptive  contact  material.  A  catalytic  action  here  takes  place, 
the  hydrogen  being  combined  with  the  previously  unsaturated  hydrocarbons,  result- 
ing in  the  production  of  oils  having  a  lower  specific  gravity  and  lower  boiling-point. 
As  examples  of  the  carrying  out  of  this  process,  Day  states  that  he  placed  100  cc. 
of  crude  petroleum  in  a  retort,  and  first  distilled  off  the  distillate  obtainable  by  the 
ordinary  course  of  distillation  obtaining  on  the  average  3  per  cent  of  distillate, 
distilling  below  150°  C.,  20  per  cent  of  distillate  distilling  between  150°  and 
300°  C.;  in  the  case  of  Mexican  oil  from  well  No.  4  of  the  Potrero  del  Llano 
district,  Mexico,  Province  of  Vera  Cruz,  and  determined  that  the  distillates, 
even  the  3  per  cent  of  naphtha  distilling  below  150°,  had  a  burnt  and  objection- 
able odor  and  would  be  characterized  by  more  than  50  per  cent  of  unsaturated 
hydrocarbons.  With  another  portion  of  the  same  crude  oil,  the  distillation  was 
repeated,  using  5  to  10  per  cent  of  sulphur.  The  result  was  an  increase  up  to 
*  U.  S.  Patent  No.  1,221,698,  Apr.  3,  1917. 


434  THE  HYDROGENATION  OF  OILS 

from  7  to  10  per  cent  in  the  yield  of  naphtha  and  up  to  30  to  35  per  cent  of  burning 
oil,  the  distillate  between  150°  and  300°  C.,  having  a  very  marked  improvement  in 
the  odor,  as  soon  as  the  sulphuretted  hydrogen  accompanying  these  distillates  was 
removed  by  the  addition  of  a  dilute  solution  of  soda.  By  the  treatment  of  the  first 
distillate  obtained,  without  the  addition  of  sulphur,  with  sulphuric  acid  it  was 
impossible  to  obtain  a  water  white  oil;  the  distillate  obtained  with  the  use  of  sulphur 
was  quite  easily  refined.  Both  samples  were  tested  as  to  the  content  of  unsaturated 
hydrocarbons,  and  it  was  found  that  the  distillate  between  150°  and  300°  C.,  by  the 
ordinary  process  contained  over  50  per  cent  of  unsaturated  hydrocarbons.  The 
test  was  carried  out  by  shaking  the  distillate  for  fifteen  minutes  with  an  equal  volume 
of  sulphuric  acid  of  1.84  gravity.  This  test  when  applied  to  the  oil  from  the  sulphur 
distillation,  showed  less  than  20  per  cent  of  unsaturated  hydrocarbons.  These 
experiments  were  carried  out  on  a  larger  scale  in  iron  stills  in  the  laboratory  of  an 
oil-refining  company  with  similar  results. 

To  convert  hydrocarbons  of  high  boiling-points  into  products  of  low 
boiling-points,  Rostin  and  Forwood  *  suggest  that  a  heavy  hydrocarbon, 
in  the  form  of  vapor,  be  mixed  with  hydrogen  sulphide  and  brought  into 
contact  with  a  substance  such  as  heated  copper  capable  of  liberating 
the  hydrogen  of  the  hydrogen  sulphide.  The  nascent  hydrogen  combines 
with  the  vapors  of  any  unsaturated  hydrocarons  produced.  The  copper 
sulphide  arising  from  the  operation  may  be  treated  with  gases  rich  in 
hydrogen,  forming  hydrogen  sulphide  and  copper. 

The  Simplex  Refining  Co.f  describe  a  cracking  process  in  which  heavy  petroleum 
oil  is  made  to  circulate,  with  or  without  pressure,  in  a  continuous  cycle,  through 
serpentine  tubes,  which  are  heated  to  the  cracking-point  of  the  oil,  and  means  are 
provided  or  the  continuous  withdrawal  of  the  resulting  vapor  and  the  addition  of 
fresh  oil  to  keep  the  circulating  oil  at  a  constant  volume.  A  portion  of  the  con- 
densed light  vapor  is  injected  into  the  residue  when  it  returns  to  the  heating  vessel. 
Advantages  claimed  for  the  process  are  regularity  in  working,  and  the  prevention  of 
overheating  and  formation  of  carbonaceous  and  viscous  deposits  within  the  tubes. 

Aromatic  compounds  are  prepared  by  dehydrogenation  of  petroleum  oils  according 
to  Mann  and  Chappell.  t  The  amount  of  benzol,  toluene,  xylene  and  other  aromatic 
compounds  in  petroleum  oil  is  increased  by  heating  the  oil  in  retorts  to  600°  to  750° 
under  a  pressure  1  to  4  in.  below  atmospheric  pressure  in  the  presence  of  500  to  800 
cu.  ft.  of  air  for  each  15  to  20  gals,  of  oil  under  treatment,  using  a  lower  oxide  of  nickel 
as  a  catalyst.  Iron  or  copper  oxides  also  may  serve  as  catalysts.  The  catalytic 
oxides  are  prepared  from  the  corresponding  nitrates  using  a  support  of  pumice  stone 
or  fire  brick.  § 

An  apparatus  for  treating  heavy  oils  and  involving  the  hydrogenation  of 
light  oils  which  are  produced  in  the  operation  has  been  devised  by  Brov/n.|| 

*  British  Patent  No.  107,034,  May  15,  1916.  See  also  Chem.  Abs.,  1918,  1558; 
Danish  Patent  22,824,  February  18,  1918. 

f  French  Patent  No.  480,147,  November  8,  1915;   J.  S.  C.  I.,  1917,  127. 
j  U.  S.  Patent  No.  1,214,204,  Jan.  30,  1917;  Chem.  Abs.,  1917, 1039;  J. S.C.I.,  1917,  332. 
§  See  also  U.  S.  Patents  Nos.  1,249,444,  Dec.  11,  1917,  and  1,257,906,  Feb.  26,  1918. 
||  U.  S.  Patent  No.  1,225,569,  May  8,  1917. 


THE  HYDROOENATION  OF  PETROLEUM 


435 


The  apparatus  is  shown  in  Fig.  56d,  in  which  a  is  a  still  or  boiler  where  the  oil 
to  be  treated  is  placed.  A  pipe  6,  which  extends  to  the  bottom  of  the  still,  is  used  for 
the  introduction  of  hydrogen.  The  vapor  produced  by  heating  the  oil  is  mingled 
with  hydrogen  and  passes  through  a  vertical  conduit  in  which  are  mounted  per- 
forated nickel  plates  c1.  These  are  supported  by  central  rods  c2.  In  the  upward 
passage  of  this  vapor  and  hydrogen,  contact  with  the  surface  of  the  nickel  is  brought 
about  and  it  is  claimed  that  the  catalytic  act  on  of  nickel  is  thus  utilized.  The  vola- 
tile products  obtained  from  the  process  are  passed  to  a  condenser.  A  water-cooling 
device  g  is  placed  about  the  conduit  c  in  order  to  main- 
tain the  temperature  sufficiently  low  to  condense  vapors 
of  heavy  oil,  this  condensate  being  returned  to  the 
still  or  boiler. 

The  cracking  of  gas  oils  in  various  atmospheres  has 
been  investigated  by  Downing  and  Pohlman.*  The 
atmospheres  used  were  nitrogen,  carbon  dioxide,  carbon 
monoxide,  hydrogen,  methane,  blue  gas,  and  a  mixture 
of  blue  gas  with  10  and  20  per  cent  of  steam,  respec- 
tively. The  effect  of  each  diluent  on  candle-power  and 
the  production  of  gas,  tar,  and  carbon  was  studied. 

The  application  of  a  high-tension  electric  dis- 
charge for  the  purpose  of  increasing  the  propor- 
tion of  fixed  gases,  in  gases  or  vapors  obtained 
by  the  cracking  of  oils  has  been  proposed  by 
Davidson  and  Ford.f 

They  state  that  the  constitution  of  the  hydrocarbon 
constituents  in  a  gas  of  this  character  may  be  materi- 
ally changed  by  the  action  of  the  electric  discharge,  the 
general  effect  being  the  formation  of  bodies  of  less 
molecular  weight  which  are  not  condensable,  thus 
increasing  the  proportion  of  fixed  hydrocarbon  constit- 
uents of  the  gas  as  compared  with  the  other  com- 
ponents, such  as  hydrogen  or  carbon  monoxide.  In  tests  which  were  made  the 
amount  of  methane  in  the  gas  was  increased  from  25  per  cent  to  about  40  per 
cent,  while  the  amounts  of  CnH2w  were  increased  from  between  7  and  10  per  cent 
up  to  20  and  23  per  cent.  In  carrying  out  this  process,  apparatus  which  is  similar 
to  that  used  for  the  electrical  precipitation  of  suspended  matter  from  gases  may  be 
employed. 

Cherry  t  descr  bes  a  me  hod  for  the  production  of  hydrocarbon  compounds  by  a 
synthetic  process  involving  the  use  of  a  high-frequency  electric  current.  Cherry 
states  that  a  rearrangement  of  the  molecular  st  ucture  of  a  hydrocarbon  can  be 
brought  about  to  change  the  boiling-point  and  gravity,  by  subjecting  the  hydrocar- 
bon to  the  silent  discharge  of  a  bipolar  oscillatory  high-frequency  electric  current 
and  the  boiling-point  and  gravity  of  the  compound  produced  can  be  varied  by 
varying  the  frequency  of  the  current  applied;  and  furthermore,  a  relatively  low-grav- 

*  Am.  Gas.  Inst.  Gas.  J.,  1917,  137,  24-26;   J.  S.  C.  I.,  1917,  125. 
f  U.  S.  Patent  No.  1,229,042,  June  5,  1917. 
j  U.  S.  Patent  No.  1,229,886,  June  12,  1917. 


FIG.  56d 


436  THE  HYDROGENATION  OF  OILS 

ity  hydrocarbon  can  be  so  changed  as  to  produce  a  compound  of  higher  gravity  and 
of  lower  boiling-point  by  subjecting  such  low-gravity  compound  to  the  electric  dis- 
charge when  the  low-gravity  hydrocarbon  is  in  a  vaporized  state  and  mechanically 
mixed  with  a  small  proportion  of  a  high-gravity  low  boiling-point  hydrocarbon 
while  a  high-gravity  low  boiling-point  hydrocarbon  (such  as  casing  head  gasoline) 
can  be  so  changed  as  to  produce  a  product  of  lower  gravity  and  higher  boiling- 
point,  by  the  action  of  the  electric  discharge  while  the  high-grav-ty  hydrocarbon 
is  in  a  vaporized  state  and  mechanically  mixed  with  a  small  proportion  of  a  rela- 
tively low-gravity  high  boiling-point  hydrocarbon. 

In  practicing  Cherry's  process,  the  vaporized  or  gaseous  hydrocarbon  material 
is  passed  through  a  bipolar  oscillatory  high-frequency  silent  electric  discharge,  and 
a  rearrangement  of  the  molecular  structure  is  stated  to  be  thereby  brought  about 
to  either  increase  or  decrease  the  proportion  of  hydrogen  in  the  resulting  compound 
without  the  waste  incident  to  destructive  distillation  The  vaporized  or  gaseous 
hydrocarbon  may  be  passed  through  a  peculiar  electric  field  or  an  electric  treating 
chamber  provided  with  separated  electrodes  between  which  the  hydrocarbon  body 
flows  so  that  this  body  will  be  subjected  for  a  more  or  less  extended  period  of  time 
to  the  silent  electrical  discharge  oscillating  back  and  forth  between  the  electrodes. 

As  an  example  of  the  application  of  the  method  to  hydrocarbon  compounds  of  the 
paraffin  series,  one  volume  of  pentadecane  (Ci5H.32)  is  introduced  into  a  still,  to 
every  two  volumes  of  methane  (CH4)  and  the  mixture  of  the  resulting  vapor  and  gas 
rising  from  the  liquid  in  the  still  is  passed  through  an  electric  field  under  proper 
heat  and  pressure  conditions,  a  resulting  liquid  product  being  drawn  from  a  condenser 
consisting  of  octane  while  the  excess  of  methane  is  separately  collected.  In  this 
instance,  approximately  the  following  reaction  is  claimed  to  take  place. 

(C16H32)+2(CH4)  =2(C8H18)  +  (CH4). 

Hirt  *  subjects  petroleum  oil  to  an  electric  arc  in  the  presence  of  hydro- 
gen under  pressure.  Oxygen  or  steam  may  be  introduced  to  remove  carbon 
deposits. 

Coast  f  mixes  petroleum  oil,  natural  gas  and  steam  and  subjects  the 
mixture  to  pressure  at  a  cracking  heat.  By  mixing  the  steam  and  gas 
with  the  oil,  a  much  "  sweeter  "  and  better  product  (gasoline)  is  obtained 
and  the  yields  are  found  to  be  improved. 

Heavy  oils,  kerosenes  and  petroleum  residues,  are  converted  into  gasoline 
and  other  volatile  oils  by  distilling  in  a  still  in  which  hydrogen  is  injected 
into  the  oil  by  a  pipe,  and  then  passing  the  resulting  mixture  of  oil  vapor 
and  hydrogen  over  nickel  plates,  the  operation  being  effected  under  a 
pressure,  e.g.,  five  to  ten  atmospheres.  The  nickel  plates  consist  of  per- 
forated discs  held  in  position  in  a  vertical  pipe  by  a  central  rod.  The 
vertical  pipe  may  also  be  lined  with  nickel.  A  cooling-system  surrounding 
this  pipe  ensures  the  return  of  heavy  oils  to  the  still.  J 

*  U.  S.  Patent  No.  1,250,879,  Dec.  18,  1917, 

t  U.  S.  Patent  No.  1,252,401,  Jan.  8,  1918. 

JDampierre,  British  Patent  No.  109,796,  Aug.  15,  1917;  Chem.  Abs.,  1918,222. 
French  Patent  No.  478,831,  Feb.  22,  1915  and  Addition  No.  20,331,  Aug.  1,  1917; 
Chem.  Abs.,  1916,  10,  2297  and  1918,  12,  1121. 


THE  HYDROGENATION  OF  PETROLEUM  437 

The  hydrogenation  of  petroleum  is  carried  out  by  Thompson  in  the 
following  manner:*  A  catalyzer  is  prepared  by  reducing;  the  oxide, 
nitrate,  carbonate,  acetate  or  formate  of  nickel  by  hydrogen  at  a  tem- 
perature of  320°  to  350°  C.,  for  one-half  to  one  hour.  The  catalyzer 
is  added  to  the  hydrocarbon  which  is  heated  in  a  cracking  still  and 
purih'ed  water  gas  or  pure  hydrogen  is  passed  through  in  large  volume 
with  strong  pressure  and  agitation.  The  resulting  mixture  of  gases 
and  vapors  is  passed  to  condensers  and  the  residual  gase's  may  be  used 
again,  if  considerable  hydrogen  is  present.  As  the  above  method  of 
making  the  catalyzer  gives  a  pyrophoric  product,  the  reduced  material 
should  be  mixed  with  oil  and  pumped  to  the  still  to  avoid  oxidation. 

Another  method  of  preparing  the  catalyzer  is:  mix  nickel  formate 
with  petroleum  oil  and  pass  the  mixture  into  the  still  while  injecting  a 
strong  current  of  water  gas.  The  passage  of  the  gas  through  the  oil 
serves  to  agitate  the  contents  of  the  receptacle  and  the  agitation  may  be 
further  supplemented  by  a  stirrer.  Thompson  states  that  the  formate 
is  decomposed,  leaving  the  nickel  in  an  almcst  colloidal  state  of 
fineness  in  the  oil.  An  amount  of  catalyzer  up  to  2  per  cent  may  be 
employed.  The  catalyzer  is  recovered  from  the  still  residue  by  washing 
with  benzol. 

Tests  conducted  by  Cross  f  with  many  catalytic  bodies  including 
aluminum  powder,  nickel,  copper,  mercury,  zinc  dust,  iron  dust,  and 
platinized  pumice  did  not  afford  increased  yields  of  light  hydrocarbons 
from  heavier  oils. 

Rittman  observes  that  many  inventors  have  made  claims  to  processes 
of  hydrogenation  of  petroleum  oils  in  connection  with  their  method  of 
"  cracking."  In  most  of  these  cases  the  hydrogen  is  derived  from 
steam  which  is  admitted  with  the  oil  or  else  is  derived  from  the  hydro- 
carbons themselves  by  employing  a  suitable  catalyzer.  J 

Jolicard  §  states  that  aromatic  hydrocarbons  are  produced  when  coal 
is  treated  at  400°  C.  with  nascent  hydrogen  in  a  furnace,  which  is  not 
heated  externally.  The  hydrogen  may  be  produced  for  example  by 
introducing  a  mixture  of  superheated  steam  and  air  at  500°  C.;  or 
carbon  monoxide  (producer  gas,  water  gas)  at  600°  C.  may  be  used  in 
place  of  all  or  part  of  the  air.  A  gaseous  catalyst,  such  a  chlorine  or 
hydrochloric  acid,  may  be  introduced,  or  a  solid  catalyst,  such  as  copper 
or  nickel,  may  be  deposited  on  the  coal. 

*  U.  S.  Patent  No.  1,160,670,  Nov.  16,  1915. 

f  Petroleum,  Asphalt  and  Natural  Gas,  Bulletin  No.  14,  Kansas  City  Testing  Labora- 
tory, 97. 

{Bulletin  114,  Bureau  of  Mines,  20. 

§  French  Patent  No.  475,433,  Feb.  17,  1914;  J.  S.  C.  I.,  1916,  36. 


438  THE  HYDROGENATION  OF  OILS 

Zerning*  passes  a  mixture  of  heavy  petroleum  and  water  (1  part 
water  to  6  to  10  parts  oil)  first  through  a  heater  to  raise  the  tempera- 
ture of  the  mixture  to  300°  to  400°  C.,  then  through  tubes  at  a  dull  red 
heat,  condenses  and  passes  the  gases  from  the  condensers  under  pressure 
into  a  body  of  petroleum  at  ordinary  temperature,  from  which  gasoline 
is  subsequently  recovered  by  distillation. 

Cracking  Tars  and  Oils.  Tars  and  mineral  oils  are  treated  for  the  pro- 
duction of  benzene,  toluene,  essences,  etc.,  by  heating  them  in  a  closed 
vessel  under  pressure  and  allowing  the  vapors  formed  to  expand  when  the 
requisite  temperature  and  pressure  have  been  reached.  In  the  case  of 
tar,  temperatures  between  90°  and  450°  and  pressures  between  2  and  18 
kg.  per  square  centimeter  are  used.  The  vapors  obtained  in  one  auto- 
clave may  be  injected  into  a  second  autoclave  containing  tar  or  oil  under 
a  different  pressure  and  temperature.  The  finely-divided  nascent  carbon 
which  separates  acts  as  a  catalyst,  the  nascent  hydrogen  also  entering  into 
reaction,  f 

The  residue  from  the  manufacture  of  oil  gas  may  be  treated  directly  with 
hydrogen  to  form  new  hydrocarbon  compounds  which  are  capable  of 
further  decomposition.  J 

In  some  experiments  made  by  Davidson  §  on  the  heat  decomposition 
of  a  mixture  of  ethane  and  propane  from  natural  gas  it  was  found 
that  the  metals  nickel,  iron  and  cobalt  hindered  the  production  of 
aromatic  hydrocarbons  but  promoted,  to  a  marked  degree,  the  forma- 
tion of  hydrogen  and  carbon. 

*  U.  S.  Patent  No.  1,183,266,  May  16,  1916. 

t  Soc.  Lyonnaise  des  Eaus  et  de  1'Eclairage.  British  Patent  No.  9,728,  July  3,  1915; 
Chem.  Abs.,  1917,  95. 

J  Rinker,  Canadian  Patent  No.  182,104,  Feb.  5,  1918;  Chem.  Abs.,  1918,  763. 
§  J.  Ind.  Eng.  Chem.  1918,  901. 


CHAPTER   XIX 
THE   HYDROGEN   PROBLEM   IN   OIL   HARDENING 

Oleic  acid  and  hydrogen  combine,  molecule  for  molecule,  to  yield 
stearic  acid  according  to  the  reaction: 


Thus  282  pounds  of  oleic  acid  require  2  pounds  (or  about  0.7  per 
cent)  of  hydrogen  for  the  production  of  284  pounds  of  stearic  acid, 
and  similarly  the  transformation  of  olein  into  stearin  requires  the 
use  of  about  0.68  per  cent  hydrogen.* 

One  thousand  cubic  feet  of  hydrogen  weigh  approximately  5.6 
pounds,  hence  a  pound  of  olein  calls  for  a  little  over  0.1  of  an  ounce 
of  hydrogen  equivalent  to  approximately  2500  cubic  feet  of  hydrogen 
per  ton  (of  2000  pounds)  of  olein.  Thus  by  weight  only  a  relatively 
small  quantity  of  hydrogen  is  needed,  while  by  volume  the  amount 
required,  of  course,  is  considerable.! 

*  The  amount  of  hydrogen  required  for  complete  conversion  is  given  by  Sachs 
(Zeitsch.  f.  angew.  Chem.,  1913,  94,  784)  as  7.4  kilos  or  85  cubic  meters  hydrogen 
per  1000  kilos  oleic  acid.  1000  kilos  of  linoleic  acid  having  two  double  bonds  call 
for  14.2  kilos,  or  170  cubic  meters  of  hydrogen.  1000  kilos  of  linoleic  with  three 
double  bonds  need  21.6  kilos,  or  289  cubic  meters  of  hydrogen,  while  a  like  weight 
of  clupanodonic  acid  with  its  four  double  bonds  requires  29  kilos,  or  348  cubic  meters 
of  hydrogen.  The  hydrogen  requirements  per  ton  of  some  of  the  fats  enumerated 
by  Sachs  are  as  follows: 

Cubic  meters 

Cocoanut  oil  ..............................................         7.8 

Tallow  ...................................................  33.57 

Olive  oil  ..................................................  68.80 

Oleic  acid  .................................................  88.80 

Corn  oil  ..................................................  143.75 

Dr.  Holde  observes  (Seifen.  Ztg.  (1912),  918)  that  oleic  acid,  the  most  important 
constituent  of  all  semi-drying  liquid  oils,  requires  only  2  parts  of  hydrogen  to  282 
parts  of  oil  in  order  to  get  stearic  acid,  while  linoleic  and  linolenic  acid  require 
4  and  6  parts  respectively  to  280  and  278  parts.  Ricinolic  acid,  which  contains  one 
atom  of  oxygen  more  than  oleic  acid,  forms  an  oxystearic  acid  which  has  a  very  high 
melting  point,  but  which  also  only  contains  2  atoms  more  of  hydrogen  than  the 
original  acid.  The  glycerides  of  stearic  or  palmitic  acid  naturally  remain  unchanged 
throughout  the  operation. 

t  According  to  Linde  (Production  of  Hydrogen,  Third  Int.  Cong,  of  Refrigeration, 
1913)  six  to  ten  cubic  meters  of  hydrogen  are  required  for  hardening  one  hundred 
kilos  of  oil. 

439 


440  THE  HYDROGENATION  OF  OILS 

The  following  tabulation  shows  the  nature  of  the  reaction  in  several 
cases : 

Oleic  Acid C18H3402  +  2  H 

Linolic  Acid Ci8H32O2  +  4  H 

Linolenic  Acid Ci8H3002  +  6  H 


Clupanodonic  Acid Ci8H2802  +  8  H 


Stearic  acid 


(Ci8H3302)3C3H5  +  6  H          =          (C18H3502)3C3H5 
Olein  Stearin 


2H  C22H4402 

Erucic  acid  Behenic  acid 

Ci8H34O3  +  2  H         =          Ci8H36O3 
Ricinoleic  acid  Hydroxystearic  acid 

One  of  the  problems  in  the  hydrogenation  field  is  that  of  a  cheap 
supply  of  pure  hydrogen.  The  demand  for  hydrogen  in  various 
directions  has  increased  of  late  and  undoubtedly  this  will  lead  to 
improvements  in  the  manufacture  of  the  gas. 

The  two  methods  now  most  favored  in  the  hydrogenation  of  oils 
are  the  iron-sponge  steam  process  and  the  electrolytic  method.  For 
large  plants  the  iron-sponge  steam  process  is  preferred,  but  it  is  rela- 
tively complicated  and  scarcely  to  be  recommended  for  plants  calling 
for  1000  cubic  feet  of  hydrogen,  or  less,  per  hour. 

In  the  electrolysis  of  brine  to  make  caustic  soda  and  bleach,  there 
exists  a  by-product  of  hydrogen  sufficient  in  amount  to  treat  au 
enormous  quantity  of  oil.  To-day  a  good  portion  of  this  hydrogen  is 
allowed  to  go  to  waste.  Eventually  it  may  be  used,  to  some  extent 
at  least,  for  hydrogenation  purposes.  One  electrolyic  plant  in  this 
country  is  producing  about  one  ton  of  hydrogen  daily.  Another 
plant  generates  nearly  one-half  a  ton,  while  a  third  concern  discharges 
into  the  air  nearly  300,000  cubic  feet  each  day.*  In  spite  of  the  vast 

*  Similar  conditions  exist  abroad,  Blum  reporting  (Met.  and  Chem.  Eng.  (1911), 
157)  that  enormous  amounts  of  hydrogen  gas  are  produced  in  the  large  works  for 
the  production  of  caustic  soda  and  chlorine  by  electrolysis  of  common  salt  solutions. 
The  hydrogen  gas  is  set  free  together  with  the  caustic  soda  at  the  cathode.  The 
quantities  are  so  large,  compared  with  the  demand  which  exists  at  present  for  hydro- 
gen, that  most  of  the  hydrogen  gas  is  passed  unused  into  the  air.  The  Griesheim- 
Elektron  Company  in  Germany  produces  daily  20,000  cubic  meters  of  hydrogen 
of  about  90  to  97  per  cent  purity.  In  this  case  the  cost  of  the  gas  is  practically 
that  of  its  compression  and  storage.  Special  railway  cars  are  built  in  Germany 
for  the  transportation  of  500  cylinders  containing  2750  cubic  meters  of  hydrogen 
gas.  The  cost  of  shipment  of  the  cylinders  is  so  great  that  the  distribution,  of 
course,  is  only  local,  as  regards  consumption  on  the  large  scale.  The  Zeppelin  Ga- 
rage in  Frankfort  is  supplied  with  hydrogen  by  means  of  a  high-pressure  main  from 
Griesheim. 


THE  HYDROGEN  PROBLEM  IN  OIL  HARDENING          441 

amount  of  by-product  hydrogen  obtainable,  it  appears  that  oil  manu- 
facturers prefer  to  install  hydrogen-generating  equipment  in  their 
present  works,  rather  than  to  ship  oil  to  a  source  of  waste  hydrogen 
and  conduct  hardening  operations  at  some  relatively  remote  point. 

In  consequence  the  present  methods  of  preparing  hydrogen  are  being 
carefully  scrutinized  and  new  systems  for  the  generation  of  the  gas 
are  being  studied  and  developed.  For  this  reason  the  whole  subject 
of  the  production  of  hydrogen  is  here  reviewed  at  some  length,*  the 
proposed  technical  methods  for  its  generation  being  classified  as 
follows : 

A.  Water  gas  as  a  source  of  hydrogen. 

1.  Replacement  of  carbon  monoxide  by  hydrogen. 

2.  Liquefaction  and  other  methods  for  the  removal  of  carbon 

monoxide. 

B.  Decomposition  of  hydrocarbons. 

C.  Action  of  steam  on  heated  metals. 

D.  Wet  processes  and  the  decomposition  of  hydrates. 

1.  Action  of  acids  on  metals. 

2.  Decomposition  of  water  by  miscellaneous  chemicals. 

3.  Electrolysis  of  water. 

4.  By-product  hydrogen. 

The  hydrogen  problems  involved  in  the  hydrogenation  of  oils  are 
discussed  by  Walter  f  who  states  that  a  plant  for  oil  hardening  cannot 
well  be  installed  by  small  concerns,  but  only  by  those  having  power- 
ful financial  resources,  because  the  cost  of  equipping  for  an  adequate 
supply  of  hydrogen  represents  so  great  an  outlay.  If  water  gas  or 
coke  oven  gas  containing  40  to  50  per  cent  hydrogen  could  be  used  the 
matter  would  present  a  different  aspect.  Water  gas  contains  on  the 
average : 

Per  cent 

Hydrogen 50 

Carbon  monoxide 41 

Carbon  dioxide 4 

Nitrogen 4.5 

Methane 0.5 

A  plant  for  the  manufacture  of  water  gas  is  much  cheaper  than  one 
for  making  technically  pure  hydrogen.  Reckoned  on  the  hydrogen 
content  the  cost  of  production  of  water  gas  is  very  much  lower  than 
that  of  pure  hydrogen. 

*  Brahmer,  Chemie  der  Gase,  Frankfort,  1911,  contains  much  useful  informa- 
tion on  the  production  of  hydrogen.  The  subject  of  hydrogen  production  on  a 
commercial  scale  is  treated  by  Lepsius  in  Monifceur  Scientifique,  1912,  493-500. 

t  Seifen.  Ztg.  (1913),  4. 


442  THE  HYDROGENATION  OF  OILS 

Coke  oven  gas  contains  about  the  following: 

Per  cent 

Hydrogen 46 

Nitrogen 15 

Carbon  monoxide 7 

Methane 20 

Ethylene 2 

Carbon  dioxide 4 

This  gas  may  be  obtained  in  large  quantities  at  low  cost  in  the  neighborhood  of 
coke  oven  plants.  Many  of  the  patents  relating  to  the  hydrogenation  of  oils  refer 
to  the  use  of  gas  mixtures  containing  hydrogen  as  well  as  to  hydrogen  gas  in  a  pure 
state.  These  statements,  Walter  argues,  appear  apparently  only  as  a  precaution  in 
order  to  preclude  others  from  making  application  for  patent  protection  on  the  use 
of  hydrogen-containing  gases  in  the  place  of  pure  hydrogen.  He  regards  the  investi- 
gation of  these  hydrogen-containing  mixtures  as  never  having  been  properly  followed 
out,  but  thus  far  the  results  obtained  are  not  promising. 

Carrying  out  the  hydrogenation  process  with  hydrogen-containing 
gases  involves:  (1)  the  catalyzer  must  not  become  contaminated 
with  poisons;  (2)  the  process  must  proceed  in  spite  of  the  presence 
of  foreign  gases;  (3)  foreign  gases  must  not  injure  the  oil. 

Carbon  monoxide  and  nitrogen  in  the  pure  state  apparently  do  not 
injure  the  usual  catalyzers  in  the  least.  As  to  the  remaining  impur- 
ities the  sulfur  compounds  are  catalyzer  poisons.  It  has  been  noted 
with  water  gas  that  the  catalyzer  loses  its  activity  much  sooner  than 
when  pure  hydrogen  is  employed.  Foreign  gases,  which  are  indiffer- 
ent in  a  chemical  sense,  of  course  dilute  the  hydrogen  with  which 
they  may  be  mixed,  and  when  one  is  working  with  a  dilute  in  place 
of  a  concentrated  reagent,  the  action  usually  is  slower.  In  this  con- 
nection investigation  shows  that  with  increasing  dilution  of  the  hydro- 
gen employed,  the  time  required  for  treatment  lengthens,  a  result 
which,  of  course,  ordinary  practice  would  indicate  is  to  be  expected. 
Also  hardening  cannot  easily  be  carried  as  far  with  hydrogen-contain- 
ing gases  as  with  pure  hydrogen.  It  can  be  stated  as  a  general  rule 
that  in  oil  hardening  the  hydrogen  conducted  into  the  oil  is  not  wholly 
absorbed,  but  goes  as  a  stream  of  gas  through  or  in  contact  with  the 
oil,  so  a  considerable  proportion  of  the  hydrogen  introduced  is  not 
used.  When  one  is  using  water  gas  in  place  of  hydrogen,  the  former 
gives  up  only  a  portion  of  its  hydrogen  to  the  oil.  The  hydrogen 
available  to  the  oil  is  thus  proportionately  less  than  with  ordinary 
hydrogen  gas,  and  repeated  conveyance  of  the  partially-used  water 
gas  through  the  oil  is  as  good  as  useless  because  of  the  great  reduc- 
tion in  the  proportion  of  hydrogen. 

Since  only  a  part  of  the  hydrogen  contained  in  water  gas  may  be 
utilized,  it  is  necessary  to  employ  relatively  a  much  larger  quantity 
of  the  latter.  Of  the  50  per  cent  or  so  of  hydrogen  contained  in 


THE  HYDROGEN  PROBLEM  IN  OIL  HARDENING          443 

water  gas,  according  to  Walter,  only  about  one-third  or  approximately 
17  per  cent  of  the  total  gas  is  used.  To  secure  the  same  effect  600 
cubic  feet  of  water  gas  in  place  of  100  cubic  feet  of  hydrogen  are  re- 
quired, in  which  case  about  500  cubic  feet  of  spent  gas  results.  -The 
spent  gas,  of  course,  should  not  be  thrown  away  as  this  would  be 
wasteful  and  arrangements  must  be  made  for  its  use  in  heating, 
lighting  or  power  applications.  It  is  not  always  convenient  to  thus 
make  use  of  such  a  large  volume  of  hydrogen-spent  gas;  furthermore 
it  is  necessary  to  make  all  the  pipes  and  connections  larger  by  six- 
fold than  when  concentrated  hydrogen  is  employed,  which  means  an 
additional  expense. 

Finally  there  is  the  question  as  to  whether  or  not  the  foreign  gases  * 
contained  in  water  gas  exert  any  detrimental  influence  upon  the  har- 
dened oil;  whether  they  do  not  during  the  process  bring  about  side 
reactions.  As  regards  carbon  monoxide  f  and  carbon  dioxide  no 
chemical  action  on  oils  or  fatty  acids  under  these  conditions  is  known, 
yet  eventually  catalyzers  may  be  employed  which  cause  side  reactions. 
If  the  hardened  oil  is  to  be  used  for  technical  purposes  such  reactions 
probably  need  not  be  feared,  but  for  edible  purposes  this  may  not 
obtain.  In  this  connection  Bomer  has  laid  down  the  condition  in  oil 
hardening  that  the  hydrogen  employed  must  be  pure  when  the  fat  is 
to  be  used  for  edible  purposes.  Thus  when  using  water  gas  in  place 
of  hydrogen,  a  number  of  difficulties  are  likely  to  arise  in  large  scale 
operation  and  the  seeming  financial  advantage  on  close  inspection 
shrinks  considerably,  practically  leaving  the  field  to  technically  pure 
hydrogen,  t 

*  The  addition  of  small  quantities  of  a  second  gas  to  a  pure  gas  markedly  reduces 
the  rate  of  diffusion  in  liquids,  according  to  Barns  (Chem.  Abs.  (1913),  3871). 

f  Caro  (Seifen.  Ztg.  (1913),  852)  considers  the  presence  of  carbon  monoxide  in 
hydrogen  used  for  hardening  fats  with  nickel  catalyzers  to  be,  under  some  circum- 
stances, injurious  to  the  catalyzer.  Maintaining  the  temperature  of  the  oil  during 
hydrogenation  above  200°  C.  is  said  to  be  beneficial,  as  any  nickel  carbonyl  formed 
will  be  at  once  decomposed  at  that  temperature. 

t  Goldschmidt  (Seifenfabr.,  32,  713)  states  that  a  good  and  cheap  source  of  hydro- 
gen gas  is  one  of  the  greatest  problems  connected  with  the  process;  that  such 
impurities  in  the  gas  as  arsenic,  phosphorus,  hydrogen  sulfide,  mineral  acids,  carbon 
bisulfide,  chloroform  and  acetone  poison  catalysts  of  the  platinum  group;  while 
sulfur,  chlorine,  bromine  and  iodine  unfavorably  affect  those  of  the  nickel  group. 

Fry  states  that  negative  hydrogen  has  been  shown  to  act  as  a  reducing  agent, 
since  it  naturally  tends  to  revert  to  its  ordinary  state,  positive  hydrogen,  which 
change  is  accompanied  by  the  liberation  of  electrons.  (J.  S.  C.  I.,  1914,  271.) 


CHAPTER  XX 

WATER  GAS  AS  A  SOURCE  OF  HYDROGEN  AND  THE 

REPLACEMENT   OF   CARBON   MONOXIDE 

BY  HYDROGEN 

Many  suggestions  have  arisen  for  the  production  of  hydrogen  from 
water  gas,  involving  replacement  of  the  carbon  monoxide  present  by 
hydrogen  through  the  reaction 

CO  +  H2O  =  C02  +  H2. 

Because  of  the  incompleteness  of  the  reaction,  those  methods  proposed 
which  do  not  take  cognizance  of  the  accumulation  of  carbon  dioxide 
and  consequent  repression  of  the  progress  of  the  reaction  have  not 
been  particularly  successful.  The  reaction  is  a  reversible  one  and 
unless  means  are  taken  to  remove  the  carbon  dioxide  as  formed,  the 
resulting  gas  mixture  contains  hydrogen,  carbon  dioxide  and  carbon 
monoxide  usually  in  such  proportion  as  to  be  too  costly  of  purification 
for  handling  on  the  large  scale.  In  consequence  lime  or  other  alkali 
has  been  suggested  for  absorbing  the  carbon  dioxide.  These  sugges- 
tions appear  in  the  patents  to  Tessie  Du  Motay  and  the  Chemischen 
Fabrik  Greisheim-Elektron,  as  will  be  pointed  out  in  a  more  detailed 
manner  in  the  following. 

Engels  *  has  made  a  careful  study  of  the  reaction  between  carbon 
monoxide,  water  vapor  and  lime.  The  investigations  show  that  the 
most  suitable  temperature  lies  between  450°  to  550°  C.  Below  450°  C. 
the  reaction  progresses  too  slowly,  while  above  550°  C.  the  conversion 
does  not  go  to  completion  or  side  reactions  occur.  Engels  studied  the 
effect  of  additions  of  an  oxide,  such  as  iron  oxide,  to  the  lime  in  order 
to  catalytically  hasten  the  reaction  and  found  its  course  to  be  much 
improved  by  the  addition  of  a  few  per  cent  of  such  catalyzer.  The 
reaction  is  exothermic  so  no  further  external  heating  is  necessary  after 
the  conversion  has  begun. 

In  1880  Tessie  du  Motay  devised  a  process  for  the  production 
of  hydrogen  from  water  gas.f  The  latter  gas  mixed  with  steam  is 

*  Uber  die  Wasserstoffgewinnung  aus  Kohlenoxyd  und  Kalkhydrat,  Disserta- 
tion, Karlsruhe,  1911. 

t  U.  S.  Patents  229,338,  229,339  and  229,340,  June  29,  1880. 

444 


WATER  GAS 


445 


passed  into  a  converter  containing  lime  where  hydrogen  and  calcium 
carbonate  are  formed.  Fig.  57  shows  a  plan  view  of  the  apparatus, 
in  which  A  is  a  water-gas  generator,  B  represents  purifiers  in  which 


FIG.  57. 


sulfur  is  removed,  C  designates  superheaters  where  steam  is  mixed 
with  the  water  gas.  The  preheated  mixture  then  passes  to  a  converter 
shown  in  Fig.  58.  The  inclined 
passageways  of  the  latter  are 
filled  with  lime  in  contact  with 
which  the  reaction 

CO  +  H20  =  C02  +  H2 

C02  +  CaO  =  CaC03, 

progresses,  yielding  hydrogen 
gas.  In  lieu  of  water  gas,  coal 
gas  or  the  vapor  of  naphtha 
may  be  similarly  treated. 

The  process  of  the  Chem. 
Fabrik  Greisheim-Elektron,  re- 
ferred to  above,*  involves  mix- 
ing water  gas  with  an  excess  of 
steam  and  passing  this  mixture  over  lime  or  hydrated  lime  to  which 
about  5  per  cent  of  iron  powder  has  been  added.  The  lime  is  heated 
to  approximately  500°  C.  in  an  upright  retort  fitted  with  an  agitator. 
The  following  reaction  takes  place: 

Ca  (OH)2  +  CO  =  CaC03  +  H2, 
*  Zeitsch.f.  angew.  Chem.  (1912),  2401;   British  Patent  2523,  Feb.  2,  1909. 


FIG.  58. 


446  THE  HYDROGENATION  OF  OILS 

with  evolution  of  heat,  and  the  reaction  chamber  is  cooled  so  that 
the  temperature  does  not  exceed  500°  C.,  or  the  temperature  at  which 
calcium  carbonate  commences  to  dissociate.  The  carbonate  is  re- 
generated by  subsequent  calcination.*  The  presence  of  water  vapor 
or  of  lime  in  the  hydrated  condition  is  essential  for  the  reaction.! 
If  absent  or  present  in  insufficient  quantities  the  carbon  monoxide 
is  absorbed  by  the  lime  without  the  formation  of  hydrogen.  In  the 
absence  of  water  the  reaction  runs  according  to  the  following  equation : 
CaO  +  2  CO  =  CaC03  +  C. 

According  to  the  statement  of  Lepsius  hydrogen  of  97.5  per  cent 
purity  is  obtained  at  a  cost  of  about  2  to  2.5  cents  per  cubic  meter. 

The  production  of  hydrogen  by  the  action  of  carbon  monoxide  and 
steam  on  quicklime  is  regarded  by  Levi  and  Piva  t  to  be  dependent  on 
the  intermediate  formation  of  calcium  formate. 

Merz  and  Weith  §  have  noted  that  when  moist  carbon  monoxide 
is  passed  over  soda  lime  heated  to  300°  C.  or  over,  hydrogen  is  formed. 
A  simple  process  for  the  production  of  hydrogen  based  on  the  observa- 
tions of  Merz  and  Weith  has  been  put  forward  by  the  Societe  generate 
des  Nitrures  in  Paris.  A  mixture  of  producer  gas  and  water  gas  is 
treated  in  the  usual  way  to  remove  carbon  dioxide  and  is  then  passed 
over  hot  lime,  which  treatment  yields  a  mixture  of  nitrogen  and  hydro- 
gen free  from  carbon  monoxide.  The  composition  of  the  hydrogen- 
nitrogen  mixture  may  be  adjusted  by  using  different  proportions  of 
the  producer  gas  and  water  gas.|| 

Jerzmanowski  f  makes  a  hydrogen-containing  gas  with  apparatus  shown  in  Fig.  59. 

A  kiln  B  filled  with  lime  is  raised  to  a  high  temperature  by  burning  producer  gas 
from  the  generator  A.  As  soon  as  a  sufficient  heat  is  attained  in  B,  an  injector  H 
blows  into  B  steam  and  petroleum,  which  are  decomposed  chiefly  into  hydrogen 
and  carbonic  acid  along  with  small  quantities  of  carbonic  oxide,  marsh  gas  and 
other  impurities.  The  gases  pass  through  a  cooler  C  to  the  gasometer  D,  and  thence 
to  purifiers.** 

*  The  Chemische  Fabrik  Griesheim-Elektron  (British  Patent  13,049,  June  3,  1912) 
mix  steam  with  gas  containing  carbon  monoxide  and  pass  the  mixture  upwards 
through  towers  packed  with  pieces  of  lime  and  heated  to  between  400°  and  700°  C. 
The  lime,  when  exhausted  owing  to  conversion  into  calcium  carbonate,  can  be  re- 
generated in  situ  by  diverting  the  stream  of  gases  and  recalcining. 

f  U.  S.  Patent  989,955,  April  18,  1911,  to  Ellenberger,  assigned  to  the  Chemische 
Fabrik  Griesheim-Elektron,  discusses  these  reactions. 

t  J.  S.  C.  I.,  1914,  310. 

§  Ber.  (1880),  719.     See  also  Ber.  1880,  31. 

li  Sander,  Zeitsch  f.  angew.  Chemie  (1912),  2406. 

1  J.  S.  C.  I.,  1884,  560. 

**  The  New  York  Oxygen  Company  produce  hydrogen  by  heating  together  anthra- 
cite and  slaked  lime.  On  passing  an  excess  of  steam  over  the  residue  in  the  retorts 
the  reverse  action  sets  in  and  the  slaked  lime  is  reproduced.  This  sequence  may  be 
continued  many  times  without  renewing  the  materials.  (J.  S.  C.  I.,  1887,  92.) 


WATER  GAS 


447 


By  another  process  steam  is  allowed  to  act  on  carbon  or  carbonaceous  matter 
to  which  both  an  alkali  compound  and  lime  have  been  added,  the  effect  of  the  addi- 
tions according  to  Dieffenbach  and  Moldcnhauer  (British  Patent  8734,  April  11, 
1910)  being  to  lower  the  temperature  of  decomposition  and  to  give  hydrogen  free 
from  compounds  of  carbon  and  oxygen.  For  example,  100  kilos  of  charcoal  or  coke, 
impregnated  with  a  10  per  cent  solution  of  potassium  carbonate,  are  mixed  with 
500  kilos  of  quicklime,  and  the  mixture  is  decomposed  py  steam  at  550°  to  750°  C. 


FIG.  59. 


They  also  claim  (British  Patent  7718,  March  30,  1910)  the  employment  of  other 
alkali  compounds  —  such  as  chlorides  and  sulfates  —  for  the  same  purpose.  The 
fuel  is  impregnated  with  a  solution  of  the  alkali  compound  and  dried,  or,  if  practical, 
the  fuel  is  coked  after  the  addition  of  such  compound.  A  comparatively  small 
amount  of  oxygen  may  be  introduced  along  with  the  steam  for  the  purpose  of  main- 
taining the  required  temperature  inside  the  decomposition  apparatus.  Granulated 
coal  or  coke  may  be  treated  with  a  solution  of  an  alkali  silicate  or  carbonate  and  the 
mixture  briquetted  and  subjected  to  the  action  of  superheated  steam  at  temperatures 
from  550°  to  750°  C.* 

Hembert  and  Henry  f  pass  superheated  steam  in  a  fine  spray  over 
coke  heated  to  redness,  whereby  a  mixture  of  hydrogen  and  carbon 
monoxide  is  formed.  This  mixture  is  led  into  a  second  retort  filled 
with  fireproof  materials,  also  heated  to  redness.  In  the  second 
retort  steam  is  allowed  to  enter  heated  to  its  point  of  dissociation. 
These  gases  act  upon  one  another,  hydrogen  and  carbon  dioxide  being 
formed.  The  carbon  dioxide  may  be  absorbed  by  milk  of  lime.  In 
this  way  3200  cubic  meters  hydrogen  are  said  to  be  obtained  from 
1  ton  of  coke. 

In  the  production  of  a  mixture  of  hydrogen  and  carbon  dioxide  by  the  action  of 
steam  on  carbonaceous  substances  or  on  water  gas,  Sauer  (German  Patent  224,862, 
May  9,  1907)  proposes  to  use  an  excess  of  steam  and  to  superheat  this  to  such  a 
degree  that  it  suffices  to  maintain  the  proper  reaction  temperature,  in  order  to 
ensure  the  production  of  a  gas  of  uniform  composition.  For  example  in  the  action 
of  steam  on  coal,  the  latter  is  not  blown  alternately  with  air  and  steam,  but  the 

*  French  Patent  417,929,  April  25,  1910. 
f  Compt.  Rend.  (1885),  101,  797. 


448  THE  HYDROGENATION  OF  OILS 

steam  is  superheated  to  such  a  degree  that  when  the  process  is  once  started  it  is 
supposedly  carried  on  continuously  by  aid  of  the  heat  of  the  steam  alone.* 

For  treating  hydrogen  and  carbon  compounds  to  oxidize  the  carbon 
to  carbonic  acid,  in  which  form  it  may  be  readily  eliminated,  leaving 
pure  hydrogen,  Moore  |  brings  the  hydrogen  and  carbon  compounds 
in  a  suitably  divided  state  (generally  as  a  gas  or  fine  spray)  into  con- 
tact with  heated  oxide  of  iron,  manganese,  copper,  tin,  lead  or  zinc, 
in  the  presence  of  a  jet  of  superheated  steam.  During  the  operation 
the  oxides  are  said  to  be  alternately  reduced  and  reoxidized,  acting  as 
carriers  of  oxygen  between  the  steam  and  the  carbon  compounds,  so 
that  the  carbon  present  is  converted  into  carbon  dioxide,  and  leaves 
the  chamber  in  which  this  is  effected  mixed  with  the  hydrogen  origi- 
nally present  and  that  resulting  from  the  decomposition  of  the  steam. 
The  carbon  dioxide  may  be  removed  by  any  known  method,  such  as 
absorption  by  lime,  or  by  water  under  pressure,  or  by  a  solution  of 
alkaline  carbonate. 

Mond  and  Langer  (British  Patent  12,608,  Sept.  1,  1888)  bring  carbonic  oxide  or 
gaseous  hydrocarbons  into  contact  with  metallic  nickel  at  a  temperature  of  350°  to 
400°  C.,  or  with  metallic  cobalt  at  400°  to  450°  C.,  when  decomposition  takes  place 
into  carbon  and  carbonic  acid  or  hydrogen,  the  carbon  combining  with  the  metal. 
If  now  steam,  at  a  moderate  temperature,  be  introduced  this  carbon  combines  with 
oxygen  to  produce  carbonic  acid,  with  simultaneous  formation  of  free  hydrogen. 
These  various  reactions  take  place  simultaneously  when  the  steam  is  passed  through 
the  apparatus  along  with  the  carbonic  oxide  or  hydrocarbon,  the  ultimate  products 
being  carbonic  acid  and  hydrogen.  The  former  can  be  eliminated  by  any  suitable 
means,  such  as  by  washing  with  milk  of  lime.  The  cobalt  or  nickel  surfaces  may 
be  obtained  by  impregnating  pumice  stone  with  a  solution  of  the  metal,  and  reducing. 

Similarly  Elworthy  |  heats  a  mixture  of  water  gas  and  steam  in  the 
presence  of  such  metals  as  nickel  or  iron  to  a  sufficiently  high  temper- 
ature to  induce  the  reaction, 

CO  +  H20  =  C02  +  H2, 

whereby  the  hydrogen  originally  present  in  the  water  gas  is  increased 
by  a  volume  equal  to  that  of  the  carbon  monoxide  contained  in  it. 
The  resulting  carbon  dioxide  is  removed  by  absorption  by  water  under 
pressure,  or  by  alkalis,  or  by  other  known  means. 

Ellis  and  Eldred  §  generate  a  hydrogen-containing  gas  as  follows: 

*  Green  (British  Patent  13,510,  July  13,  1895)  states  he  obtains  hydrogen  from 
water  by  an  improved  process,  "which  consists  in  burning  steam  with  hydrogen  gas, 
or  with  carburetted  hydrogen,  or  carbon  monoxide  within  a  suitable  chamber." 

t  J.  S.  C.  I.,  1885,  450. 

t  French  Patent  355,324,  June  17,  1905. 

§  U.  S.  Patent  854,157,  May  21,  1907. 


WATER  GAS  449 

Producer  gas,  generated  by  blowing  air  through  a  producer  charged 
with  fuel,  is  led  through  a  superheating  chamber  filled  with  checker- 
work  of  refractory  material.  The  gas  is  then  passed  under  a  boiler 
and  burned  to  generate  steam.  Water  gas  is  mixed  with  steam  and 
passed  through  the  superheater  to  convert  the  carbon  monoxide  into 
dioxide.  The  mixture  of  carbon  dioxide  and  hydrogen  is  then  com- 
pressed; the  former  is  separated  in  the  liquid  condition  and  the  latter 
is  collected  separately.  The  process  is  rendered  continuous  by  repeat- 
ing the  above  steps  alternately.* 

The  essential  feature  of  a  process  devised  by  Dieffenbach  and 
Moldenhauer  f  is  that  a  mixture  of  steam  with  a  hydrocarbon  or 
other  suitable  organic  compound  is  heated  to  the  temperature  of 
reaction,  or  kept  in  contact  with  a  catalytic  body  for  only  a  short 
time  and  is  then  suddenly  cooled  or  removed  from  the  catalyzer,  in 
order  that  the  carbon  dioxide  formed  shall  have  little  or  no  opportu- 
nity for  being  reduced  to  carbon  monoxide.  From  the  resulting  mix- 
ture of  hydrogen  and  carbon  dioxide,  the  latter  can  easily  be  removed, 
leaving  more  or  less  pure  hydrogen.  A  suitable  way  of  carrying  out 
the  process  is  to  use  as  catalyzer  wire  gauze  of  nickel,  cobalt,  platinum, 
etc.,  disposed  transversely  to  the  direction  of  flow  of  the  gases,  and 
heated  electrically  to  the  requisite  temperature.  Instead  of  using 
external  heating,  the  required  temperature  may  be  attained  partly 
or  entirely  by  combustion  of  a  portion  of  the  hydrocarbon  by  means 
of  admixed  oxygen. 

Naher  and  Muller  J  prepare  water  gas  by  blowing  superheated 
steam  into  a  generator  filled  with  coke,  which  has  been  heated  to 
about  1000°  C.,  and  exhausted,  and  the  gas  produced,  mixed  with 
superheated  steam,  is  passed  over  a  contact  mass  of  rhodium-  or  palla- 
dium-asbestos at  800°  C.  The  resulting  hydrogen  then  is  freed  from 
the  accompanying  carbon  dioxide. 

Carbon  monoxide  and  steam  are  caused  to  interact  at  300°  to 
600°  C.  under  a  pressure  of  4  to  40  atmospheres  in  the  presence  of  a 
catalyst,  such  as  iron,  nickel,  or  the  like,  with  the  production  of 
carbon  dioxide  and  hydrogen,  the  former  being  removed  by  absorp- 
tion according  to  a  process  devised  by  the  Badische  Company.§ 

In  order  to  better  effect  the  reaction  betweeen  carbon  monoxide 
and  water  vapor  in  the  presence  of  heated  catalytic  material  and  to 
carry  on  the  operation  continuously  the  Badische  Company  inject 

*  Ellis  and  Eldred  employ  nickel,  iron  or  manganese  as  catalytic  material, 
f  German  Patent  229,406,  June  3,  1909. 
t  German  Patent  237,283,  Sept.  30,  1910. 
§  British  Patent  26,770,  Nov.  21,  1912. 


450  THE  HYDROGENATION  OF  OILS 

oxygen  or  air  into  the  reaction  chamber  thus  securing  the  necessary 
heating  effect.* 

Pullman  and  Elworthy  f  generate  a  mixture  of  hydrogen  and  car- 
bon dioxide  by  passing  superheated  steam  in  excess  over  red-hot  coke 
or  charcoal  contained  in  a  cast-iron  retort,  and  the  mixed  gases  after 
cooling  are  led  through  a  number  of  porous  pipes  made  of  plaster  of 
Paris  or  unglazed  earthenware  where  they  are  separated  to  a  great 
extent  by  diffusion,  the  hydrogen  passing  more  rapidly  through  the 
porous  walls  of  the  pipes  than  the  carbon  dioxide. 

After  leaving  the  diffusing  apparatus  the  nearly  pure  hydrogen  is  compressed 
into  suitable  vessels  partially  filled  with  water  to  absorb  most  of  the  remaining  carbon 
dioxide.  On  opening  the  valves  of  the  vessels  the  hydrogen  rapidly  escapes,  and 
may  be  collected  in  a  suitable  holder  and  then  given  a  final  purification,  either  by 
washing  with  water  in  a  scrubber  or  by  passing  it  over  some  absorbent  for  carbonic 
acid,  such  as  damp  hydrate  of  lime,  or  through  milk  of  lime.  Instead  of  separating 
the  mixed  gases  by  diffusion,  they  may  be  taken  from  the  cooling  apparatus  direct 
and  compressed  in  strong  metal  vessels  partially  filled  with  water.  The  carbonic 
acid  being  much  the  more  soluble,  on  opening  the  vessels  hydrogen  at  first  escapes 
rapidly  and  may  be  collected,  the  carbonic  acid  being  afterwards  collected  in  a 
separate  receiver.  The  gases  may  be  submitted  to  this  operation  several  times  over, 
and  finally  purified  as  above.  Or  instead  of  using  water,  glycerine  or  hydrocarbon 
oils  which  absorb  more  gas  and  part  with  it  more  slowly  may  be  used. 

That  complete  replacement  of  carbon  monoxide  by  hydrogen  in  processes  in- 
volving heating  water  gas  and  steam  is  impossible  because  of  the  conditions  of  equilib- 
rium which  obtain,  is  discussed  by  Gautier  (Bull.  Soc.  Chim.  (1906),  35,  929)  who 
refers  to  the  work  of  Boudouard  (BuU.  Soc.  Chim.  (1901),  25,  484).  The  latter 

CO 
determined  the  ratio  f^r,  in  the  equilibrium  between  carbon  monoxide,  steam,  carbon 


dioxide,  and  hydrogen  at  different  temperatures;  and  Hahn  (Z.  Physik  Chem.  (1903), 
42,   705;  44,   513;   (1904),  48,  735)   determined  the  coefficient  K  =  C°  X 


X  n.2 

at  different  temperatures.  When  a  current  of  carbon  monoxide  mixed  with  a  vary- 
ing excess  of  steam  is  passed  through  a  porcelain  tube  heated  to  1200°  to  1250°  C., 
at  the  rate  of  about  1  liter  of  the  mixed  gases  per  hour,  or  when  a  dry  mixture  of 
equal  volumes  of  carbon  dioxide  and  hydrogen  is  similarly  treated  at  1300  degrees, 
the  reaction  proceeds  until  the  volume  of  hydrogen  is  about  double  that  of  carbon 
monoxide.  The  reactions  correspond  with  the  equations: 

3  CO  +  3  H2O  =  CO  +  H2O  +  2  H2  +  2  CO2, 
3C02  +  3H2     =  CO  +  H20  +  2H2  +  2CO2. 

Under  these  conditions,  any  mixture  of  carbon  monoxide,  steam,  hydrogen  and 
carbon  dioxide  tends  towards  the  composition,  CO  +  H2O  +  2  H2  +  2  CO2.  Small 
quantities  of  formic  acid,  but  no  formaldehyde,  are  produced. 

Additional  matter  by  Gautier  appears  in  Comptes  rendus  (1910),  150,  1564, 
considering  the  reaction  particularly  from  the  reverse  standpoint,  that  is,  the  reduc- 

*  British  Patent  27,117,  Nov.  25,  1912;  Chem.  Zeit.  Rep.  (1913),  696. 
t  British  Patent  22,340,  Dec.  21,  1891. 


WATER  GAS  451 

tion  of  carbon  monoxide  by  hydrogen.  The  results  show  that  by  heating  carbon 
monoxide  in  the  presence  of  hydrogen,  water  is  actually  formed.  The  reduction 
begins  approximately  at  200°  C.  The  maximum  formation  of  water  is  between 
1100°  and  1200°  C.* 

By  a  process  of  the  Badische  Company  f  water  gas  is  passed  with 
an  excess  of  steam  over  heated  finely-divided  metals  of  the  iron 
group,  especially  iron,  cobalt  and  nickel,  or  their  oxides,  and  the  car- 
bon dioxide  formed  is  eliminated  from  the  gaseous  reaction  product. 
The  catalyst  is  best  prepared  by  the  addition  of  appropriate  diluents 
or  binding  agents,  organic  or  inorganic,  which  may  be  such  as  to  give 
off  gas  on  heating  so  as  to  increase  the  porosity.  For  example,  dry 
precipitated  ferrous  carbonate  may  be  made  into  a  plastic  mass  with 
lime,  water,  potassium  hydroxide  and  ferric  nitrate,  and  the  mix- 
ture dried  and  heated  to  500°  C.  A  reaction  temperature  of  prefer- 
ably not  over  600°  C.  is  maintained  by  adjusting  the  temperature  of 
the  gases  before  they  enter  the  contact  chamber. 

Bosch  and  Wild  t  produce  hydrogen  by  passing  carbon  monoxide 
and  steam  over  a  catalytic  material  consisting  of  nickel  or  cobalt  or 
non-metallic  refractory  material,  which  may  be  moulded  into  porous 
blocks. 

Temperature  ranges  of  from" about  400°  to  600°  C.,  may  be  used.  Iron  may  be  sub- 
stituted for  nickel  and  cobalt  provided  it  is  supported  on  an  inert  substance.  Bosch 
and  Wild  have  found  that  it  is  possible  to  carry  out  the  reaction  to  good  advantage 
by  passing  carbon  monoxide  and  steam  over  a  form  of  catalytic  agent  containing  at 
least  30  per  cent  of  finely-divided  nickel  and  more  than  70  per  cent  of  non-metallic, 
indifferent,  refractory  and  porous  material,  the  catalytic  agent  being  porous  and 
shaped  into  the  form  of  blocks,  tubes,  rods,  or  the  like.  It  is  stated  that  excellent 
results  can  be  obtained  by  preparing  an  oxide,  hydroxide  or  carbonate  of  nickel, 
either  by  precipitation  from  solutions  of  its  salts,  or  by  heating  suitable  salts,  such 
for  instance  as  the  oxalate  or  nitrate,  while  avoiding  too  high  a  temperature,  then 
moulding  the  resulting  products  and  if  necessary  heating  before  introduction  into 
the  reaction  furnace.  The  production  of  hydrogen  by  the  aid  of  such  catalytic 
agents  can  be  carried  out  by  adding  an  excess  of  steam  to  a  gas  containing  carbon 
monoxide  and  then  passing  the  mixture  of  gases  over  the  catalytic  agent  and  subse- 
quently removing  the  carbon  dioxide  which  has  been  formed.  The  action  of  the 
catalytic  agent  is  very  satisfactory  at  temperatures  of  about  from  400°  to  500°  C., 
or  even  less  down  to  350°  C.,  but  temperatures  above  650°  C.  should  be  avoided.  It 
is  advisable  to  keep  both  the  catalytic  agent  and  the  gases  free  from  substances  such 
as  sulphur  and  chlorine  which  have  a  deleterious  action.  The  following  illustrates 
the  method  of  producing  a  catalytic  agent  and  of  producing  hydrogen  by  its  means. 
Prepare  a  nickel  hydroxide  paste  by  introducing  5  parts  of  25  per  cent  milk  of  lime 

*  Met.  and  Chem.  Eng.  (1911),  511. 
t  French  Patent  459,918,  July  2,  1913. 

tU.  S.  Patents  Nos.   1,113,096,    Oct.  6,   1914;    1,113,097,    Oct.  6,   1914;    1,115,776, 
Nov.  3,  1914. 


452  THE  HYDROGENATION  OF  OILS 

into  7  parts  of  molten  nickel  nitrate,  add  10  parts  of  precipitated  green  nickel  oxide 
(NiO),  knead  the  whole  well,  mould  into  the  shape  of  briquettes  and  heat  up  to  500°  C. 
Then  place  the  briquettes  in  a  suitable  furnace  and  pass  through  it  a  mixture  of  pure 
carbon  monoxide  with  an  excess  of  steam,  while  maintaining  a  temperature  of 
about  500°  C.,  and  then  extract  the  carbon  dioxide  from  the  resulting  gases. 

A  catalyzer  containing  cobalt  is  prepared  as  follows: 

Mix  together  10  parts  of  finely-divided  cobalt  oxide  (prepared  by  raising  cobalt 
nitrate  to  a  red  heat),  1  part  of  calcined  magnesia,  and  2  parts  by  volume  of  a  50 
per  cent  magnesium  nitrate  solution.  Press  the  mixture  into  small  briquettes,  dry 
and  heat  up  to  500°  C. 

When  using  an  iron  catalyzer,  the  following  formulas  are  recommended : 

(1)  Add  a  solution  of  100  parts  of  calcined  sodium  carbonate  in  500  parts  of 
water  to  a  solution  of  250  parts  of  ferrous  sulphate  in  500  parts  of  water.     Filter 
off  the  precipitate  and  wash  it,  and  then,  without  drying,  mix  it  with  5  parts  of 
slaked  lime  and  dry  until  a  paste  is  obtained  which  is  then  kneaded,  rolled  out,  cut 
into  cubes,  dried,  and  heated  at  about  500°  C.     Instead  of  slaked  lime,  an  agent 
can  be  employed  which  decomposes  upon  being  heated,  such  for  instance  as  14  parts 
of  calcium  nitrate,  or  a  mixture  of  14  parts  of  calcium  nitrate  and  6  parts  of  ammo- 
nium nitrate. 

(2)  Knead  to  a  paste  10  parts  of  finely-divided  iron  oxide,  such,  for  instance,  as 
the  crocus  martis  of  commerce,  and  a  solution  of  4  parts  of  aluminum  nitrate  in  4 
parts  of  water.     Form  this  paste  into  pieces  of  the  desired  shape,  which  then  dry 
and  heat  at  400°  C.  in  a  current  of  air.     In  this  example,  the  aluminum  nitrate 
solution  can  be  replaced  by,  for  instance,  a  solution  of  3.5  parts  of  magnesum  nitrate 
in  3.5  parts  of  water. 

(3)  Melt  40  parts  of  crystallized  ferric  nitrate  at  from  50°  to  60°  C.  and  stir  ^n  a 
mixture  of  5  parts  of  caustic  lime,  15  parts  of  water  and  2  parts  of  caustic  potash. 
Then  mix  this  product  with  50  parts  of  precipitate  which  has  been  obtained  according 
to  (1)  and  then  dried,  work  the  mixture  in  a  kneading  machine  until  a  plastic  mass 
is  obtained,  roll  this  out,  cut  it  into  cubes,  dry  it  and  heat  at  500°  C.     Sometimes 
it  is  desirable  to  pass  over  it  a  current  of  air  or  of  carbon  dioxide. 

(4)  Heat  and  stir  ferric  nitrate  at  180°  C.  until  its  nitric  acid  is  almost  completely 
driven  off,  pass  the  residue  through  the  finest  sieve  and  mix   10  parts  of  this  with 
1  part  of  calcined  magnesia,  moistening  it  with  a  solution  of  1  part  of  potassium 
carbonate  in  1.6  parts  of  water.     Press  the  mass  into  briquettes,  dry  them  and  heat 
to  about  600°  C. 

(5)  Boil  2.5  parts  of  wheat  starch  with  15  parts  of  water  until  a  stiff  paste  is 
obtained,  stir  in  1  part  of  potassium  carbonate,  add  20  parts  of  iron  oxide  obtained 
by  carefully  heating  iron  oxalate  to  a  temperature  not  exceeding  600°  C.     Knead 
the  whole  until  a  plastic  mass  is  obtained,  form  it  into  briquettes,  dry  it  and  heat  at 
about  600°  C.     In  this  example,  gum  tragacanth,  dextrine,  or  gum  arabic,  can  be 
employed  instead  of  the  starch. 

(6)  Mix  9  parts  of  ferric  oxide  hydrate  with  1  part  or  more,  of  ferric  oxalate  and 
then  work  up  the  mixture  to  a  paste  with  a  solution  of  2.5  parts  of  calcium  nitrate 
in  2  parts  of  water.     Press  the  paste  into  suitable  shapes  and  dry  slowly  in  a  current 
of  air  at  about  500°  C.     Then  pass  a  mixture  of  pure  carbon  monoxide  with  an 
excess  of  steam  over  the  catalytic  agent  thus  obtained,  while  maintaining  a  tempera- 
ture of  about  500°  C. 

(7)  Pass  a  current  of  carbon  monoxide  mixed  with  steam  over  iron  in  a  state 
of  fine  division  which  has  been  preferably  moulded  in  a  briquette  press,  at  the 


WATER  GAS  453 

same  time  gradually  heating  the  catalytic  agent,  but  avoiding  temperatures  above 
000°  C. 

(8)  Mix  ferric  oxide  hydrate  with  sufficient  concentrated  calcium  nitrate  solu- 
tion to  obtain  a  paste  of  suitable  consistency,  then  bring  this  paste  into  suitable 
shapes  and  dry  it  in  the  contact  furnace  while  gradually  raising  the  temperature  to 
about  500°  C.     Then  pass  a  mixture  of  carbon  monoxide  and  steam  over  the  cata- 
lytic agent,  while  avoiding  temperatures  above  600°  C.     Even  if  the  gases  are  passed 
rapidly  through  the  reaction  furnace,  an  almost  complete  conversion  of  the  carbon 
monoxide  into  carbon  dioxide  takes  place. 

(9)  Heat  ferric  nitrate  to  about  200°  C.  so  as  to  convert  it  into  the  oxide.     Moisten 
the  latter  with  aluminum  nitrate  solution  and  then  mould  it  into  suitable  shapes  and 
heat  it  at  about  400°  C.,  until  the  nitrous  gases  are  driven  off.     Then  place  the  cata- 
lytic agent  in  the  contact  furnace  and  pass  a  mixture  of  carbon  monoxide  and  steam 
through  the  furnace  while  avoiding  temperatures  above  600°  C.* 

Contact  masses  prepared  by  saturating  pumice  with  a  solution  of  nickel  or  cobalt 
chloride  and  subsequently  igniting,!  are  stated  by  the  Badische  Co.J  not  to  be  sat- 
isfactory in  the  production  of  hydrogen  from  carbon  monoxide  and  steam.  Good 
yields  of  hydrogen  are  obtained,  however,  by  using  contact  masses  prepared  by  im- 
pregnating suitable  materials  with  relatively  small  quantities  of  solutions  of  nickel 
salts  free  from  halogens  and  sulphur. 

The  Badische  Company  §  obtains  hydrogen  by  the  catalytic  double 
decomposition  of  carbon  monoxide  or  gases  containing  carbon  monoxide 
with  steam,  with  the  employment  of  nickel. 

Ordinarily  while  using  nickel  contact  material  an  undesired  by-product  |l  is 
formed.  To  prevent  the  formation  of  methane  there  may  be  employed  mixed  con- 
tact masses,  consisting  of  an  excess  of  iron  or  its  oxides  with  the  nickel  or  its  oxides. 
Other  elements  or  their  compounds  which  have  active  properties,  are  added  advan- 
tageously. The  specified  contact  masses,  even  at  low  temperatures  effect  a  rapid 
and  extensive  decomposition  and  are  to  be  preferred  to  nickel  because  of  their  sta- 
bility and  slight  sensitiveness  to  accidental  increases  in  temperature  and  to  impuri- 
ties in  the  gas  mixture.  The  contact  mass  is  applied  preferably  in  the  form  of  porous 
pieces.  A  suitable  mass  is  obtained  by  precipitating  a  solution  of  40  parts  iron 
nitrate,  5  parts  nickel  nitrate  and  5  parts  chromium  nitrate  (all  free  from  chlorine), 
with  potassium  carbonate  and  thoroughly  washing.  The  mass  is  then  formed, 
dried,  and  a  water-gas-steam  mixture  is  conducted  over  it  at  400°  to  500°.  The 
amount  of  nickel  can  be  increased  or  diminished.  In  a  modification  the  principal 
portion  of  the  carbon  monoxide  can  be  removed  with  a  suitable  catalyzer  at  500°  to 
600°  and  the  gas,  while  still  hot,  is  freed  from  hydrogen  sulphide  by  passage  over 

*  A  mixture  of  gases  and  steam  containing  carbon  monoxide  is  conducted  at  an  elevated 
temperature  over  contact  masses  which  comprise  at  least  30  per  cent  of  finely-divided 
metals  of  the  iron  group  (iron,  nickel  or  cobalt)  deposited  chemically  from  metal  salt 
solutions  and  which  are  made  up  into  porous  bodies  with  the  addition  of  organic  diluents 
or  binders;  Badische  Co.,  Austrian  Patent  No.  72,430,  Sept.  11,  1916. 

t  See  French  Patent  No.  463,114,  of  1913;   J.  S.  C.  I.,  1914,  313. 

J  German  Patent  No.  297,258,  Sept.  11,  1914.  Addition  to  German  Patent  No.  292,615, 
J.  S.  C.  I.,  1917,  873. 

§  German  Patent,  No.  282,849,  Dec.  4,  1913;   Chem.  Abs.  1915,  2437. 

II  Methane. 


454  THE  HYDROGENATION  OF  GAS 

copper,  or  the  like,  and  then,  with  the  addition  of  steam,  it  is  conducted  over  the 
new  contact  mass  at  350°  to  400°.* 

Metals  of  the  iron  group  such  as  iron,  cobalt  and  nickel,  or  their  oxides  or  mix- 
tures of  these  in  the  form  of  porous  pieces,  briquettes,  cubes,  rods,  tubes,  etc.,  are 
prepared  with  the  aid  of  inorganic  and  organic  diluents  or  binders  by  the  Badische 
Company.f  Substances  may  be  added  which,  upon  heating,  generate  gas  or  wholly 
volatilize.  Even  at  400°  to  500°  and  lower  the  action  of  the  contact  masses  is  excep- 
tionally good.  A  suitable  contact  mass  may  be  prepared  as  follows:  A  solution  of 
250  parts  ferrous  sulphate  in  500  parts  water  is  precipitated  by  means  of  a  solution 
of  100  parts  calcined  soda  in  500  parts  water.  The  precipitate  is  washed,  com- 
pressed, and  intimately  mixed  without  previous  drying  with  5  parts  of  slaked  lime 
and  then  dried  to  obtain  a  mass  which  can  be  kneaded.  This  mass  is  rolled  out, 
cut  into  cubes,  dried  and  heated  to  500°.  The  Badische  Company,  §  also  employ,  as 
catalyst,  spathic  iron  ore,  or  a  hydroxide  iron  ore,  which  has  not  at  any  stage  of  the 
process  been  subjected  to  a  temperature  appreciably  higher  than  650°.  The  catalyst 
may  be  employed  in  the  form  of  grains,  or  may  be  made  into  shaped  pieces  with  the 
aid  of  binding  agents,  such  as  hydroxides  or  salts  or  iron,  aluminum,  etc.  The 
presence  of  phosphorus,  sulphur  or  silica  is  objectionable. 

Vignon  §  converts  the  carbon  monoxide  of  water  gas  into  methane  by  the  following 
method.  Water  gas  is  mixed  with  a  determined  quantity  of  steam  and  passed  over 
quicklime  heated  to  350°  to  1200°  C.  Below  about  850°  C.  calcium  carbonate, 
methane,  and  hydrogen  are  produced,  while  above  this  temperature  the  calcium 
carbonate  is  decomposed,  and  the  resulting  gas  also  contains  carbon  dioxide.  Small 
quantities  of  other  hydrocarbons,  such  as  ethylene,  are  also  formed. 

In  the  method  of  Bosch  and  Wild  j  |  hydrogen  is  produced  by  removing 
part  of  the  carbon  monoxide  from  water  gas  and  treating  the  residual 
gas  with  steam  under  a  pressure  of  about  60  to  600,  Ib.  per  square  inch 
while  subjected  to  the  action  of  a  catalyzer.  The  hydrogen  may  imme- 
diately be  used  under  its  original  pressure  in  making  ammonia.  More 
hydrogen  is  obtained  and  the  reaction  is  accelerated  by  producing  the 
hydrogen  under  high  pressure. 

Bosch  and  Wild  If  state  that  the  heat  necessary  to  enable  the  reaction  to  be  started 
and  also  to  maintain  the  temperature  for  the  reaction  can  be  generated  with  great 
ease,  by  supplying  oxygen  to  the  gases  when  in  contact  with,  or  on  their  way  to,  the 
catalytic  agent,  the  oxygen  entering  into  combination  with  the  combustible  gases 
and  providing  the  required  heat.  Instead  of  pure  oxygen,  air  can  be  employed 
in  those  cases  where  the  presence  of  nitrogen  in  admixture  with  the  hydrogen  is  not 
objectionable,  for  instance  when  the  hydrogen  obtained  is  to  be  employed  for  the 
catalytic  production  of  ammonia.  When  water  gas  or  other  gas  containing  hydrogen 
and  carbon  monoxide  is  employed,  and  the  oxygen  introduced  combines  with  a 

*  J.  S.  C.  I.,  1915,  716. 

t  German  Patents  No.  292,615,  July  24,  1912  and  293,943,  Feb.  11,  1913;  Chem.  Abs., 
1918,  855. 

t  Chem.  Abs.,  1916,  98;  J.  S.  C.  I.,  1915,  800;  British  Patent  No.  16,494,  July  10,  1914. 

§  French  Patent  No.  469,907,  June  2,  1913;  Chem.  Abs.,  1915,  19. 

||  U.  S.  Patent  No.  1,157,669. 

T  U.  S.  Patent  No.  1,200,805,  1916. 


WATER  GAS  455 

part  of  the  hydrogen  to  form  steam,  the  latter  can  again  take  part  in  the  reaction, 
and  consequently  the  amount  of  steam  employed  can  be  correspondingly  reduced. 
The  oxygen,  or  air,  is  supplied  directly  to  the  contact  chamber  at  one  or  more  places. 

The  process  can  be  carried  out  either  with  pure  carbon  monoxide  or  with  carbon 
monoxide  which  is  more  or  less  diluted  with  other  gases,  and  it  is  of  particular  use 
when  it  is  desired  to  free  a  mixture  of  gases,  such,  for  instance,  as  water  gas,  from 
carbon  monoxide,  since  the  conversion  of  the  carbon  monoxide  into  carbon  dioxide 
sets  free  hydrogen  which  mixes  with  the  hydrogen  of  the  water  gas.  It  is  then 
only  necessary  to  remove  the  carbon  dioxide  and  any  excess  of  steam,  in  order  to 
produce  pure  hydrogen. 

This  process  is  claimed  to  offer  great  advantages  when  gases  are  employed  which 
contain  relatively  little  carbon  monoxide,  because,  in  this  case,  the  heat  of  reaction 
is  small  and  the  difficulties  incidental  to  supplying  heat  from  the  outside  are  conse- 
quently much  exaggerated.  In  this  case,  the  supply  of  oxygen  can  be  so  regulated 
that,  during  the  combustion,  sufficient  steam  is  formed  to  enable  the  whole  of  the 
carbon  monoxide  to  be  oxidized  and  consequently  further  addition  of  steam  is  not 
necessary. 

The  Badische  Company  *  describe  a  method  or  producing  hydrogen 
in  which  contact  masses  are  used  containing  activating  substances, 
especially  oxygen  compounds  of  chromium,  thorium,  uranium,  beryllium, 
antimony,  and  the  like,  or  mixtures  of  these,  in  addition  to  the  usual  cata- 
lysts. With  such  contact  masses  the  reaction  is  practically  quan- 
titative at  a  relatively  low  temperature.  The  contact  mass  during 
preparation  or  use  should  not  be  heated  above  600°  C.  Small  quan- 
tities of  carbon  monoxide  may  be  readily  removed  from  gaseous  mix- 
tures with  the  aid  of  the  contact  masses  described. 

According  to  a  somewhat  similar  method  of  the  Badische  Company  f  a  mixture 
of  carbon  monoxide  and  steam  is  passed  over  a  mixture  containing  a  catalytic  agent 
and  a  body  which  promotes  the  activity  of  the  catalytic  agent.  Suitable  catalytic 
mixtures  consist  of  iron,  nickel,  or  cobalt  or  their  oxides,  mixed  with  oxygen  com- 
pounds of  chromium,  thorium,  uranium,  beryllium,  or  antimony;  iron  mixed  with 
less  than  its  weight  of  nickel;  iron  oxide  of  low  activity  coated  with  finely-divided 
iron  oxide  prepared  at  a  low  temperature,  or  zinc,  lead,  copper,  vanadium,  manga- 
nese or  titanium,  together  with  a  promoter.  The  contact  masses  may  be  in  the  form 
of  powder,  porous  lumps,  etc.,  and  binders,  carriers,  etc.,  may  be  added.  The  pro- 
duction of  hydrogen  is  preferably  effected  at  temperatures  not  exceeding  600°. 
Any  suitable  gas  mixtures  may  be  used,  and  the  bulk  of  the  carbon  monoxide  may 
be  first  removed  therefrom  catalytically,  or  otherwise.  Hydrogen  sulphide  may  be 
previously  removed  by  means  of  copper.  The  presence  of  chlorine,  phosphorus, 
bromine,  or  silica  in  the  catalytic  mixture  should  be  avoided,  The  following  exam- 
ples of  the  preparation  of  the  catalytic  mixtures  are  given :  A  mixed  solution  of  ferric 
and  chromium  nitrates,  with  or  without  aluminum  nitrate,  is  precipitated  by  ammo- 
nia and  the  hydroxides  are  filtered  off  and  pressed  into  suitable  shapes;  a  mixture  of 
ferric  nitrate,  ammonia  chromate,  and  thorium  nitrate,  is  heated  to  give  the  oxides; 
a  solution  of  ferric  nitrate,  nickel  nitrate,  and  chromium  nitrate  is  precipitated  by 

*  German  Patent  No.  279,582,  June  24.  1913;  J.  S.  C.  I.,  1915,  355. 
t  British,  Patent  No.  27,963,  Dec.  4,  1913;  Chem.  Abs.,  1916,  97. 


456  THE  HYDROGEKATION  OF  OILS 

potassium  carbonate  and  the  precipitate  filtered,  washed,  shaped,  and  dried;  fine 
meshed  wire  netting  is  treated  with  ferric  nitrate  solution,  and  heated  to  decompose 
the  nitrates;  chromium  nitrate  or  acetate  is  precipitated  by  ammonia,  the  hydroxide 
is  mixed  with  precipitated  zinc  oxide,  shaped  and  dried;  Beryllium  oxide  may  also 
be  used;  a  mixture  of  lead  nitrate  or  lead  acetate  and  uranium  nitrate  solution  is 
precipitated  with  ammonia,  the  precipitate  is  filtered,  made  into  lumps,  and  heated; 
copper  and  zirconium  nitrate  solution  is  precipitated  by  sodium  carbonate  or  potas- 
sium carbonate,  filtered,  the  alkali  salt  washed  out  partly  or  completely,  and  the 
product  moulded  and  dried;  mixtures  of  oxides  of  manganese  and  chromium,  titan- 
ium and  antimony,  vanadium  and  chromium  or  chromium  and  thorium  are  also 
suitable;  aluminum  oxide,  alkali  carbonates,  etc.,  may  be  added  as  binding  agents 
or  promoters;  a  solution  containing  cerium  and  chromium  nitrates  is  precipitated 
with  ammonia,  the  precipitate  filtered  off.  partly  dried,  made  into  a  paste,  shaped, 
and  dried;  other  rare-earth  salts  may  replace  the  cerium  nitrate.* 

Considerable  progress  has  been  made  in  the  production  of  hydrogen  from  water 
gas  by  reaction  between  carbon  monoxide  and  water  vapor.  A  mixture  of  water  gas 
and  steam  is  passed  over  a  contact  material  of  iron  oxide  with  oxide  of  chromium 
and  thorium  as  activating  agents.  The  reaction  takes  place  at  a  relatively  low 
temperature  which  favors  the  yield  of  hydrogen  from  the  standpoint  of  temperature 
equilibrium.  Carbon  dioxide  is  removed  by  treatment  under  pressure  with  water. 
Any  carbon  monoxide  is  eliminated  by  a  copper  chloride  solution.  The  purified 
gas  contains  about  2  per  cent  of  nitrogen  and  traces  of  methane.  The  cost  of 
manufacture  is  low,  as  regeneration  of  the  heat  due  to  reaction  suffices  for  carrying 
on  the  process,  f 

Hydrogen  is  produced,  according  to  the  Badische  Company,  by  passing  a  mixture 
of  a  hydrocarbon  and  steam  over  a  nickel  catalyst  distributed  on  a  refractory  carrier. 
Gaseous,  liquid  or  solid  hydrocarbons  may  be  used,  or  hydrocarbon  mixtures,  as 
coal  gas.  The  nickel  catalyzer  may  be  prepared  in  various  ways.  In  one  case 
fragments  of  magnesium  oxide  are  impregnated  with  nickel  nitrate  solution.  In 
another  case,  nickel  is  deposited  on  the  "carrier  by  the  decomposition  of  nickel  car- 
bonyl.  Temperatures  of  700°  and  higher  are  used.  For  example,  methane,  mixed 
with  three  to  six  volumes  of  steam,  is  passed  over  the  catalyst  at  a  temperature  of 
800°  to  1000°.  t 

Ellis  §  employs  a  method  of  making  hydrogen  involving  the  treatment 
of  lime  or  lime-material  with  carbon  monoxide,  or  gases  containing  car- 
bon monoxide.  For  example,  carbon  monoxide  is  passed  over  hydrated 
lime  or  carbon  monoxide  mingled  with  steam  is  contacted  with  lime, 
the  latter  being  heated  to  a  temperature  of  450°  to  600°  C. 

The  monoxide  takes  oxygen  from  the  water  vapor  forming  carbon  dioxide  and 
liberating  hydrogen  and  the  carbon  monoxide  combines  with  the  lime  to  form  calcium 

*See  also  German  Patent  No.  282,849;  J.  S.  C.  I.,  1915,  717;  first  addition,  dated 
June  15,  1914,  to  French  Patent  No.  459,918,  July  2,  1913;  Swiss  Patent  No.  71,803, 
Feb.  16,  1916;  Chem.  Abs.,  1916,  1918;  Norwegian  Patent  No.  26,689,  Feb.  21,  1916; 
Chem.  Abs.,  1916, 1582;  German  Patent  No.  284,176,  May  2, 1914;  Chem.  Abs.,  1915,  2803. 

t  Z.  Kompr.  fl.  Gase,  1914,  16,  187-191;  Zeitsch.  angew.  Chem.  Referat.,  1915,  203. 

j  British  Patent  No.  12,978,  June  4,  1913;  see  also  U.  S.  Patent  No.  1,128,804,  to  Mi1>- 
tasoh  and  Schneider. 

§  U.  S.  Patent  No.  1,173,417. 


WATER  GAS  457 

carbonate.  This  action  is  accelerated  by  the  presence  of  catalytic  material  such  as 
iron  oxide  and  manganese  oxide.  The  reaction  is  exothermic  and  once  the  mass 
of  lime  has  been  brought  to  the  reacting  temperature,  sufficient  heat  is  developed 
for  continuance  of  the  operation  without  the  aid  of  externally-applied  heat.  In 
fact  cooling  may  sometimes  be  required  as  the  reaction  does  not  progress  with  as 
good  yields  when  the  temperature  is  much  above  525°  or  550°  C.  Another  consider- 
ation is  the  use  of  an  excess  of  steam  which  greatly  improves  the  yield  of  hydrogen. 

Four  to  five  times  as  much  water  vapor  by  volume  as  carbon  monoxide  should  be 
present  in  order  to  effect  substantially  complete  conversion.  Difficulties  are  expe- 
rienced in  treating  lime  with  gases  to  insure  satisfactory  absorption  of  the  carbon 
dioxide,  and  it  is  desirable  to  remove  the  carbon  dioxide  as  fast  as  it  is  formed  in 
order  to  prevent  by  mass  action  the  repression  of  the  reaction  due  to  the  accumula- 
tion of  the  carbon  dioxide,  in  the  gaseous  atmosphere. 

To  carry  out  the  conditions  required  for  the  reaction  Ellis  makes  use  of  a  treating 
apparatus  comprising  a  series  of  superimposed  conveyers. 

These  conveyers  are  connected  by  chutes  so  that  the  lime  and  contact  material, 
entering  the  uppermost  conveyer,  feed  downwardly  conveyer  by  conveyer  and 
finally  discharge  from  the  lowest  section. 

The  gas  or  vapor  mixture  flows  upwardly  from  section  to  section  in  contact  with 
lime  material  which  is  constantly  but  slowly  moved  forward  in  a  direction  opposite 
to  the  flow  of  the  gases  or  vapors  and  under  these  conditions  the  carbon  monoxide 
unites  with  the  oxygen  of  the  water,  forming  carbon  dioxide,  which  combines  with  the 
lime,  thus  removing  the  carbon  dioxide,  as  such,  from  the  scene  of  the  reaction  and 
enabling  a  further  conversion  of  carbon  monoxide  into  carbon  dioxide,  so  that  the 
gases  discharging  from  the  upper  section  of  the  conveyer  may  be  practically  pure 
hydrogen  or  hydrogen  containing  only  a  small  measure  of  contaminating  products. 

The  lime  which  is  employed  for  the  operation  preferably  is  low  in  magnesia, 
as  dolomite  and  other  high  magnesia  limes  are  not  as  desirable  for  this  purpose. 
The  lime  should  be  finely  divided,  which  may  be  accomplished  by  grinding,  or  the 
lime  may  be  introduced  in  the  hydrated  form  as  a  dry  powder.  The  addition  of 
about  5  per  cent  of  finely-divided  iron  or  manganese  oxide  is  desirable  to  accelerate 
the  reaction.  The  iron  or  manganese  oxide  preferably  is  derived  by  precipitation 
as  a  hydrate  from  aqueous  solution  and  washing  and  drying  the  product. 

The  resulting  carbonated  lime  is  removed  by  a  conveyer  and  is  passed  through  a 
rotary  kiln  which  may  be  heated  by  a  producer  gas  or  a  powdered  coal  flame,  and 
the  lime  regenerated;  care  being  taken  to  not  overheat  the  iron  or  manganese  oxide 
to  such  an  extent  that  its  amorphous  condition  is  lost.  The  regenerated  lime,  espe- 
cially if  not  overheated,  may  be  used  repeatedly. 

In  place  of  carbon  monoxide  or  water  gas,  producer  gas,  or  even  the  vapors  of  oil, 
may  be  mingled  with  steam  and  passed  over  the  lime  to  effect  decomposition,  thereby 
liberating  hydrogen  both  from  the  oil  and  the  water,  forming  first  carbon  monoxide 
and  then  carbon  dioxide  which  is  absorbed  by  the  lime. 

In  the  process  of  Siedler  and  Henke,*  water  gas  or  other  gas  rich 
in  carbon  monoxide  is  mixed  with  steam  and  the  mixture  passed  over 
lumps  of  lime  arranged  in  superimposed  layers  in  a  vertical  tower 
and  maintained  at  a  temperature  of  400°  to  750°  by  heat  initially 
supplied  by  the  gas  ard  by  the  heat  of  the  reaction. 

*  Chem.  Abs.,  191G,  1708;   U.  S.  Patent  No.  1,181,264. 


458  THE  HYDROGENATION  OF  OILS 

Hydrogen  is  manufactured  according  to  Griesheim-Elektron  * 
from  carbon  monoxide,  steam  and  alkali  or  alkaline  earth. 

When  gases  containing  carbon  monoxide  and  steam  are  conducted  over  calcium 
hydrate  or  caustic  soda  at  temperatures  of  450°  to  550°  hydrogen  is  obtained. 
This  reaction  is  favored  materially  by  employing  increased  pressure  and  corre- 
spondingly increased  temperatures.  In  the  same  period  of  time  four  times  as  much 
hydrogen  can  be  secured  as  when  operating  at  atmospheric  pressure.  Either  steam 
or  a  mixture  of  steam  and  gases  containing  carbon  monoxide  is  conducted  over  a 
mixture  of  alkali  or  alkaline  earth  and  carbon,  or  a  mixture  of  steam  and  carbon 
monoxide  is  conducted,  at  an  increased  pressure,  over  alkalies  or  alkaline  earths. 
Pressures  of  10  to  100  atmospheres  and  over  are  employed.  If  gases  containing 
carbon  monoxide  are  to  be  acted  upon  alone,  good  yields  are  secured  at  five  atmos- 
pheres pressure.  With  the  use  of  lime,  a  temperature  of  600°  to  800°  is  suitable, 
and  with  the  use  of  barium  hydrate  and  alkali,  a  materially  lower  temperature  may 
be  employed.  Especial  advantages  are  secured  by  conducting  steam,  under  a 
pressure  of  ten  atmospheres  and  more,  over  a  mixture  of  lime  and  coal  or  charcoal, 
almost  pure  hydrogen  being  obtained.  Since  the  thermal  effect  is  strongly  positive, 
generally  the  application  of  heat  is  not  required  in  a  sufficiently  large  apparatus. 

A  tower  may  be  used  in  which  a  charge  of  coal  and  lime  is  placed.  The  coal 
serves  both  as  a  source  of  heat  and  for  the  decomposition  of  steam.  When  by  air 
blowing,  the  charge  has  been  brought  to  the  desired  temperature,  the  supply  of  air 
is  discontinued,  and  water  or  steam  is  conducted,  from  above,  over  the  mixture,  at 
twenty  atmospheres  pressure.  The  burned  lime  is  discharged  from  below,  mixed 
with  fresh  coal,  and  returned  to  the  process.  Brown  coal  or  charcoal  is  preferred 
since  they  react  more  quickly  and  at  lower  temperatures  than  hard  coal  and  coke. 

Vignon  f  describes  a  horizontal  or  slightly  inclined  rotary  retort 
which  is  charged  with  coal,  anthracite,  or  coke,  and  quicklime,  and  a 
mixture  produced  by  the  rotation  of  the  retort.  The  mixture  is  heated 
to  900°  to  1000°  C.  and  water  or  steam  passed  in  until  the  temperature 
falls  to  700°  C.  The  gas  is  withdrawn  and  air  passed  through  to  raise 
the  temperature  to  900°-1000°  C.  and  to  regenerate  the  lime. 

Buchanan  and  Maxted  J  prepare  hydrogen  by  passing  a  mixture  of 
carbon  monoxide  or  gases  containing  carbon  monoxide  and  steam 
over  a  catalyst  consisting  of  an  alkali  ferrite  which  has  been  lixiviated 
so  that  a  portion  of  the  alkali  is  removed;  the  alkali  ferrite  may  be 
prepared  by  roasting  ferric  oxide,  from  burnt  pyrites,  with  sodium 
carbonate.  Another  method  of  producing  hydrogen  by  Buchanan 
and  Maxted  §  depends  on  the  interaction  of  carbon  monoxide  and 
steam  in  the  presence  of  a  catalyst  consisting  of  or  containing  a 

*  German  Patent  No.  284,816,  March  14,  1914;  J.  S.  C.  I.,  1915,  1092;  Chem.  Abs., 
1916,  101. 

t  French  Patent  No.  477,083,  May  25,  1914;  J.  S.  C.  I.,  1916,  592. 

t  British  Patent  No.  6,476,  March  14,  1914;  J.  S.  C.  I.,  1915,  177;  Chem.  Abs.,  1915, 
2434. 

§  British  Patent  No.  6,477,  March  14,  1914;  Chem.  Abs.,  1915,  2434;  J.  S.  C.  I., 
1915,  552. 


WATER  GAS  459 

met  all  ic  couple;  Fe-Cu  or  Fe-Ag  couples  arc  suitable.  The  catalyst 
may  be  made  from  lixiviated  alkali  ferrite,  by  reducing  the  ferric 
oxide  therein  to  the  metallic  state  by  hydrogen,  moistening  with  a 
solution  of  copper  nitrate,  and  finally  heating,  preferably  in  a  current 
of  reducing  gas,  or  washing,  to  remove  nitrates.  Gases  containing 
carbon  monoxide  may  be  used  instead  of  carbon  monoxide  in  a  state 
of  purity.  The  couple  is  heated  to  500°  C.  while  passing  carbon 
monoxide  and  an  excess  of  air  over  it. 


CHAPTER   XXI 

LIQUEFACTION   AND   OTHER  METHODS   FOR   THE 
REMOVAL   OF   CARBON    MONOXIDE 

As  uncarburetted  or  blue  water  gas  consists  of  approximately  equal 
parts  hydrogen  and  carbon  monoxide  with  small  amounts  of  other 
gases,  much  attention  has  been  given  to  methods  of  eliminating  the 
monoxide  by  solution,  absorption  and  liquefaction.  The  cost  of 
removal  of  the  carbon  monoxide  by  solvents  such  as  cuprous  chloride 
and  the  like  appears  to  be  too  great  for  commercial  application.  As 
the  monoxide  is  relatively  easily  liquefied  by  cold  and  pressure,  while 
hydrogen  is  extremely  resistant  to  liquefaction  under  like  conditions, 
processes  have  been  devised  for  removing  carbon  monoxide  in  this  way. 
As  a  source  of  cheap  hydrogen  this  method  offers  attractive  possi- 
bilities to  concerns  requiring  large  amounts  of  the  gas.  For  small 
plants  the  relatively  high  cost  of  installation  renders  the  use  of  lique- 
faction processes  less  feasible. 

The  pioneer  work  connected  with  the  development  of  the  lique- 
faction system  towards  a  commercial  goal  should  be  credited  to  C.  E. 
Tripler,  who  apparently  was  the  first  to  devise  methods  and  apparatus 
for  large  scale  liquefaction  of  air  and  other  gases.  In  1893  Tripler 
patented  *  the  method  of  condensation  "  of  a  current  of  gas  by  ex- 
pansion of  itself  over  the  conduit  through  which  it  passes."  On  this 
idea  is  based  the  present  systems  of  separating  hydrogen  and  carbon 
monoxide  through  liquefaction  of  the  latter. 

The  principle  of  liquefaction  by  compression  with  counter-current 
cooling  is  shown  diagrammatically  in  Fig.  60.  The  reducing  valve  R 
is  so  arranged  that  on  the  side  carrying  the  receiver  B  for  the  liquefied 
product  a  pressure  of  20  atmospheres  is  maintained,  while  on  the  other 
side  the  pressure  is  held  at  200  atmospheres.  The  operation  is  as 
follows.  Air  is  drawn  from  B  by  the  compressor  K,  passing  through 
the  outer  concentric  tube  of  the  coil.  After  compression  to  200  at- 
mospheres the  air  enters  the  cooler  KG  where  the  heat  generated  by 
compression  is  absorbed.  The  cooled  compressed  air  flows  through 
the  inner  tube  of  the  coil  to  the  reducing  valve  R  where  it  is  released 

*  British  Patent  4210,  1893. 
460 


LIQUEFACTION 


461 


at  20  atmospheres.     Circulation  in  fhis  manner  is  kept  up  until  the 
temperature  is  lowered  to  the  point  of  liquefaction. 

Nitrogen  boils  at  —  193  degrees,  carbon  monoxide  at  —  190  degrees 
and  carbon  dioxide  at  —  78  degrees  while  hydrogen  boils  at  —  252  de- 
grees and  may  easily  be  retained  in  gaseous  form  at  temperatures 
which  convert  the  other  components  of  water  gas  to  liquids  or  solids.* 


£  -* 


FIG.  60. 

Apparatus  in  various  forms  has  been  devised  by  Linde,f  Claude,  Hildebrandt  and 
others  for  the  separation  of  the  components  of  mixed  gases  by  the  liquefaction  of 
the  more  easily  liquefied  constituents.  The  Hildebrandt  system,  shown  in  Fig.  61, 
consists  of  a  coil  of  pipe  of  relatively  large  diameter  through  which  two  smaller  pipes 
extend.  The  latter  are  indicated  by  1  and  7  in  the  upper  right-hand  terminus  of 
the  large  coil.  •  Gas  under  the  requisite  high  pressure  enters  at  1,  passes  along  one 
of  the  small  pipes  within  the  larger  pipe  of  the  large  coil,  emerges  at  2  and  passes 
along  the  central  riser  to  the  expansion  chamber  E.  Expansion  with  liquefaction 
occurs  here.  The  liquefied  product  flows  through  3  into  the  chamber  R  and  from 
thence  into  a  multiple  evaporating  coil  4,  which  consists  of  four  coiled  pipes  having 
openings  along  their  upper  sides.  Evaporation  of  the  more  easily  boiling  constitu- 
ents takes  place  as  the  product  flows  downwardly  along  the  evaporating  conduits. 
The  vaporized  portion  departs  through  the  perforations  of  the  coil  and  passes  through 
5  into  the  large  pipe  A,  moving  along  this  pipe  as  a  current  counter  to  the  high-pressure 
gas  entering  at  1  and  passing  out  of  the  system  by  the  horizontal  pipe  shown  on  the 
upper  right  hand.  The  liquid  fraction  collecting  in  G  flows  along  one  of  the  narrow 
pipes  to  2,  thence  through  one  of  the  narrow  pipes  in  the  large  coil,  upwardly  and 
out  at  7. 

*  The  production  of  hydrogen  by  liquefaction  is  clearly  described  by  Linde  in 
the  Proceedings  of  the  Third  Int.  Congress  of  Refrigeration,  1913.  See  also  a  very 
comprehensive  treatise  entitled,  "Lowest  Temperatures  in  Industry,"  issued  by 
Gesellschaft  fur  Lindes  Eismaschinen,  Munich. 

t  In  a  publication  entitled  "Lowest  Temperatures  in  Industry,"  it  is  stated  that 
five  plants  have  been  supplied  by  the  Linde  Co.  for  fat-hardening  purposes  and  that 


462 


THE  HYDROGENATION   OF  OILS 


Linde  makes  note  *  that  Frank  and  Caro,  with  the  aid  of  the  Linde 
firm,  have  succeeded  in  the  production  of  hydrogen  of  a  high  degree 
of  purity  from  water  gas.  Figs.  62  and  63  show  the  apparatus  dia- 
grammatically. 


FIG.  61. 


FIG.  62. 


FIG.  63. 


Compressed  water  gas  enters  by  the  innermost  tube  A,  and  is  cooled 
by  expansion  through  the  valves  and  return  of  the  cooled  gases  by  the 
middle  and  outermost  tubes  G  and  E  respectively,  until  liquefaction 
of  the  carbon  monoxide  occurs;  separation  then  takes  place,  the 
gaseous  hydrogen  escaping  through  the  valve  F  and  the  tube  G,  the 
liquid  carbon  monoxide  passing  through  the  valve  D  and  evaporating 

the  total  capacity  of  these  is  over  1000  cubic  meters  per  hour.     A  plant  in  St.  Peters- 
burg uses  100  cubic  meters;  another  in  Nishnj-Nowgorod  30  cubic  meters;  Bremen- 
Bersigheimer  Olfabriken  200  cubic  meters;   United  Soap  Works,  Ltd.,  Rotterdam, 
200  cubic  meters;  and  Ardol  Co.,  Leeds,  500  cubic  meters  per  hour. 
*  J.  S.  C.  I.,  1911,  746. 


LIQUEFACTION  463 

in  the  middle  tube.  It  was  found  impossible  to  liquefy  the  carbon 
monoxide,  however,  by  the  small  amount  of  cooling  by  internal  work 
of  a  gas  containing  so  much  hydrogen,  and  the  cooling  was  therefore 
aided,  as  indicated  in  Fig.  63,  by  cold-jacketing  the  lower  portion  of 
the  apparatus  by  means  of  a  similar  apparatus  producing  liquid  air; 
in  this  way  the  industrial  success  of  the  apparatus  was  secured,  and 
a  gas  produced,  containing  hydrogen,  97  per  cent;  carbon  monoxide, 
2  per  cent;  nitrogen,  1  per  cent.  Removal  of  the  carbon  monoxide  by 
calcium  carbide  or  soda  lime  then  yields  a  99  per  cent  hydrogen.  The 
gas  formed  from  the  liquid  contains  85  to  90  per  cent  of  carbon  mon- 
oxide, the  rest  being  chiefly  hydrogen,  and  is  an  excellent  power  gas. 

By  one  process  (Ges.  fur  Linde's  Eismaschinen  A.  G.,  French  Patent  427,983, 
March  31,  1911)  the  strongly-cooled,  compressed  gaseous  mixture  containing  hydro- 
gen is  passed  through  a  heat  interchanger  so  as  to  separate  it  into  a  gaseous  portion, 
chiefly  hydrogen,  and  a  liquid  portion,  consisting  mainly  of  impurities.  The  mix- 
ture passes  into  a  receiver,  which  is  provided  with  two  separate  systems  for  producing 
expansion;  the  liquid  portion  of  the  mixture  collects  in  the  receiver  and  is  expanded 
in  the  lower  system,  from  which  it  passes  into  the  interchanger  in  the  space  sur- 
rounding the  tube  which  conveys  the  original  mixture  into  the  receiver,  and  in  the 
opposite  direction  to  that  of  the  gaseous  current;  the  gaseous  portion  is  expanded 
in  the  upper  system  and  passed  into  the  interchanger  in  the  space  surrounding  the 
tube  which  conveys  the  mixture  expanding  from  the  lower  system.  From  the  inter- 
changer the  expanded  hydrogen  is  collected  free  from  impurities,  which  are  thus 
condensed  by  the  cold  produced  by  the  agency  of  the  above-mentioned  expansions. 
A  supplementary  refrigerating  appliance,  containing  liquid  air  or  liquid  nitrogen, 
is  used  in  conjunction  with  the  apparatus  for  the  preliminary  cooling  of  the  gaseous 
mixture. 

A  modified  form  of  the  foregoing  consists  in  removing  the  portion  of  the  gaseous 
mixture  which  is  not  liquefied,  and  comprises  chiefly  hydrogen,  without  allowing 
it  to  expand,  the  pressure  remaining  equal  to  that  to  which  the  compressed  gaseous 
mixture  has  been  brought.  Liquid  air  or  liquid  nitrogen,  used  for  refrigeration, 
is  evaporated  at  a  pressure  below  that  of  the  atmosphere,  in  order  to  obtain  a  more 
complete  separation  of  the  remaining  impurities.  The  liquid  air  or  liquid  nitrogen  is 
thus  used  only  for  the  ultimate  refrigeration  of  the  hydrogen  which  has  already  been 
freed  from  the  main  quantity  of  condensable  gases.  Also,  the  hydrogen,  before  it  is 
brought  to  the  expansion  apparatus  may  be  subjected  to  slight  heating  in  a  counter- 
current  device,  by  means  of  the  compressed  gaseous  mixture  which  has  not  yet 
been  fractionated.* 

Frank  f  cools  water  gas  in  a  suitable  apparatus  sufficiently  to  liquefy 
the  carbon  monoxide  and  dioxide,  which  are  then  separated.  If  the 
water  gas  has  been  produced  at  a  low  temperature,  and  contains 

*  Ges.  fur  Linde's  Eismaschinen  A.  G.,  First  Addition,  to  French  Patent  427,983, 
March  31,  1911.  See  also  U.  S.  Patents  to  Carl  von  Linde  1,020,102  and  1,020,103, 
March  12,  1912;  1,027,862  and  1,027,863,  May  28,  1912;  727,650  and  728,173, 
May  12,  1903. 

t  British  Patent  26,928,  Nov.  27, 1906. 


464 


THE  HYDROGENATION  OF  OILS 


chiefly  carbon  dioxide,  with  but  little  carbon  monoxide  besides  hydro- 
gen, it  may  be  completely  liquefied,  and  the  hydrogen  recovered  by 
fractional  distillation.  In  either  case  the  hydrogen  resulting  is  further 
purified  by  being  conducted  over  calcium  carbide  at  a  temperature  of 
over  300°  C.* 

The  arrangement  of  a  plant  under  the  Linde-Frank-Caro  system  f 
is  shown  in  Fig.  64.     In  this  illustration  a  is  a  water-gas  generator  to 


FIG.  64. 


which  air  from  the  blower  b  and  steam  from  the  boiler  c  is  alternately 
supplied,  d  is  a  scrubber  and  e  a  gasometer.  1  is  a  water-gas  com- 
pressor, 2  an  air  compressor  and  3  a  refrigerating  apparatus.  Fore- 
coolers  for  drying  the  air  and  water  gas  are  shown  at  4.  A  water-gas 
separator  indicated  by  5  is  also  used  for  the  liquefaction  of  air.  A  gas 
engine  6  operated  by  the  rejected  carbon  monoxide  (collected  in  gasom- 
eter 7)  furnishes  power  for  running  the  compressors.  8  represents 

*  Frank  (J.  Gasbeleucht,  June  10,  1911)  has  recommended  (see  J.  S.  C.  I.,  1911, 
746)  that  apparatus  for  the  production  of  pure  hydrogen  and  other  gases  by  cooling 
and  liquefaction  should  be  installed  at  gas  works  making  water  gas  to  enable  hydro- 
gen to  be  supplied  on  the  large  scale. 

f  Gesellschaft  fur  Lindes  Eismaschinen. 


LIQUEFACTION 


465 


FIG.  65.    Linde  hydrogen  apparatus. 

purifiers  for  removal  of  carbon  dioxide  *  and  9  soda-lime  purifiers  for 
the  ultimate  purification  of  the  hydrogen.  Before  purification  by 
soda  lime  the  gas  consists  of 

Per  cent 

Hydrogen   97-97.5 

Carbon  monoxide 1 . 7-2 

Nitrogen 1.0-1.8 

and  after  such  treatment  the  composition  is: 

Per  Cent 

Hydrogen 99.2-99.4 

Nitrogen 0.6-0.8 

An  apparatus  for  separating  hydrogen  from  the  other  constituents 
of  water  gas  is  shown  in  Fig.  66. f 

*  The  Bedford  method  of  removing  carbon  dioxide  by  washing  the  gas  under 
high  pressure,  with  water,  is  used. 

t  Maschinenbau-Anstalt  Humboldt,  French  Patent  445,883,  July  8,  1912. 


466 


THE  HYDROGENATION  OF  OILS 


Water  gas  is  compressed  until  the  carbon  monoxide  is  liquefied,  impurities  such 
as  carbon  dioxide  are  removed  in  the  usual  manner,  and  the  mixture  of  hydrogen 
and  carbon  monoxide  is  introduced  into  a  separator  a,  from  which  it  passes  through 

a  concentric  tube  system  b,  in  counter- 
current  to  the  separated  cold  gases,  to  a 
worm  c,  situated  in  an  evaporator  d,  which 
is  partly  filled  with  liquid  carbon  monox- 
ide. The  mixture  expands  by  way  of  the 
valved  injector  e,  into  a  condenser  h,  at 
the  bottom  of  which  the  liquid  carbon 
monoxide  accumulates,  while  gaseous  hy- 
drogen ascends  into  a  riser  i.  Here  the 
entrained  carbon  monoxide  vapor  settles 
by  virtue  of  its  greater  density,  allowing 
pure  hydrogen  to  pass  by  way  of  an  over- 
flow-pipe k  into  the  concentric  tube  sys- 
tem 6  and  out  of  the  separator  at  I.  The 
liquid  carbon  monoxide,  which  accumu- 
lates in  h,  passes  through  an  overflow-pipe 
?n,  controlled  by  a  regulator  o,  down  along 
the  chamber  n,  into  the  evaporator  d, 
leaving  in  the  upper  part  of  n  any  ac- 
companying  hydrogen,  which  may  be  with- 
drawn. The  liquid  carbon  monoxide, 
which  accumulates  at  the  bottom  of  d,  is 
evaporated  by  the  worm  c,  and  the  gaseous 
carbon  monoxide  escapes  by  way  of  the 
pipe  p,  through  the  tubular  system  6,  and 
out  of  the  apparatus  at  I.  By  making  the  riser  i,  and  chamber  n,  of  the  requisite 
height,  the  two  gases  may  be  obtained  of  the  required  degree  of  purity. 

A  process  for  the  separation  of  hydrogen  from  carbon  dioxide  has 
been  proposed  by  Claude.*  The  hydrogen  containing  carbon  dioxide 
is  subjected  to  a  pressure  of,  say,  30  atmospheres,  and  is  then  passed 
through  heat-exchangers  wherein  it  meets  cold  gas  passing  in  an  oppo- 
site direction.  The  temperature  of  the  gaseous  mixture  falls  progres- 
sively, and  the  carbon  dioxide  gradually  liquefies.  The  temperature 
should  not  be  low  enough  for  the  production  of  solid  carbon  dioxide. 
The  counter-current  of  cold  gas  may  be  the  non-liquefied  portion  of  the 
compressed  gaseous  mixture,  the  cold  end  of  the  heat-exchanger  being 
cooled  externally  by  suitable  means.  Claude  f  partially  liquefies 
water  gas  or  analogous  gaseous  mixture  so  as  to  give  pure  hydrogen 
and  carbon  monoxide  containing  hydrogen  in  solution,  and  the  latter 
mixture  is  submitted  to  the  action  of  heated  slaked  lime  or  other 


FIG.  66. 


*  French  Patent  375,991,  May  28,  1906. 
t  French  Patent  453,187,  March  28,  1912. 


LIQUEFACTION  467 

material  capable  of  reacting  to  yield  more  or  less  pure  hydrogen  which 
is  added  to  the  water  gas  about  to  be  treated.* 

Elworthy  f  separates  carbon  dioxide  from  a  mixture  of  gases  derived 
from  water  gas,  containing  hydrogen,  carbon  monoxide,  methane,  and 
carbon  dioxide  by  simple  compression  of  the  cooled  gaseous  mixture, 
or  by  compression  followed  by  expansion,  when  the  carbon  dioxide  is 
liquefied  or  solidified,  and  can  be  removed.  The  gases  escaping  from 
the  apparatus  are  utilized  for  cooling  the  incoming  gases. 

Jouve  and  Gautier  {  propose  to  pass  water  gas  through  a  porous 
partition,  such  as  unglazed  porcelain,  in  order  to  separate  hydrogen 
by  reason  of  its  rapid  power  of  diffusion.  It  is  said  that  by  one  such 
operation  the  percentage  of  carbon  monoxide  may  be  reduced  from 
45  to  8  per  cent. 

According  to  Elsworthy§  water  gas  may  be  passed  through  a  centrifugal  gas 
separator,  which  is  said  to  remove  the  bulk  of  the  hydrogen,  almost  free  from 
other  gases. 

Separation  of  hydrogen  by  an  absorption  method  is  recommended 
by  Vignon.  ||  Water  gas,  cooled  and  washed,  is  treated  in  a  scrubber 
with  an  acid  or  alkaline  solution  of  cuprous  chloride,  thus  absorbing 
carbon  monoxide;  the  hydrogen  is  thereby  obtained  free  from  carbon 
monoxide.  The  latter  gas  is  recovered  by  heating  the  solution  or 
subjecting  it  to  reduced  pressure,  and  the  cuprous  chloride  is  then  used 
again.  The  carbon  monoxide  may  be  utilized  by  mixing  it  with  air 
and  burning  it  in  the  water-gas  generator,  so  as  to  supply  the  heat 
necessary  for  the  formation  of  the  water  gas,  or  this  may  be  effected 
by  burning  the  monoxide  in  a  vertical  shaft,  filled  with  refractory 
material,  fixed  in  the  center  of  the  generator. 

Frank  ^  passes  dry  water  gas  over  calcium  carbide  at  a  temperature 
above  300°  C.  Carbon  monoxide  reacts  with  the  carbide  forming 
calcium  oxide,  calcium  carbonate  and  carbon,  while  the  nitrogen 
present  is  converted  into  calcium  cyanamide.** 

*  The  Claude  Company  (Chem.  Ztg.  Rep.  (1913),  521;  French  Patent  453,187, 
March  28,  1912)  indicate  that  the  present  attainable  yield  (about  50  per  cent)  of  hy- 
drogen by  the  liquefaction  system  is  increased  and  the  loss  through  solution  of  hydro- 
gen in  carbon  monoxide  is  diminished  if  the  carbon  monoxide  gas  carrying  hydrogen 
is  subjected  to  the  action  of  hydrated  lime  to  form  calcium  carbonate  and  hydrogen 
and  the  impure  hydrogen  thus  secured  is  mixed  with  water  gas  and  further  treated 
in  a  similar  manner. 

t  First  Addition,  June  16,  1906,  to  French  Patent  355,324,  June  17,  1905. 

j  French  Patent  372,045,  1906. 

§  British  Patent  10,581,  May  5,  1906. 

II  French  Patent  389,671,  April  27,  1908. 

H  French  Patent  371,814,  1906. 
**  Thorpe  Diet.  App.  Chem.  III.,  61. 


468 


THE  HYDROGENATION  OF  OILS 


Frank  conducts  water  gas  through  milk  of  lime  to  remove  carbon 
dioxide,  then  through  cuprous  chloride  in  hydrochloric  acid  solution 
to  remove  carbon  monoxide  and  over  heated  calcium  carbide  to  re- 
move nitrogen  as  cyanamide.  The  carbide  also  removes  traces  of 
carbon  monoxide  and  dioxide  with  separation  of  carbon  in  a  finely- 
divided  condition.  The  cuprous  chloride  solution  is  regenerated  by 
exposing  to  reduced  pressure  to  remove  the  monoxide.*  Subsequently 
Frank  stated  f  that  the  expense  of  carbide,  or  of  cuprous  compounds 
or  other  means  of  absorbing  carbon  monoxide,  was  found  to  be  too 
great  and  ultimately  he  was  led  to  adopt  the  method  of  removal  by 
liquefaction. t 

Claude  §  states  that  in  the  manufacture  of  hydrogen  by  partial 
liquefaction,  1 1  hydrogen  of  99  per  cent  purity  can  be  obtained  from 
purified  water  gas,  but  the  process  is  open  to  objection  that  the  maxi- 
mum volume  of  hydrogen  obtainable  is  equal  only  to  one-half  the  vol- 
ume of  water  gas  employed. 

In  practice  this  yield  is  reduced  owing  to  part  of  the  hydrogen  being  held  in  solu- 
tion in  the  carbon  monoxide.  Also  an  excessively  minute  adjustment  at  the  exit 
cock  for  the  liquefied  carbon  monoxide  escaping  from  the  liquefying  apparatus  is 


FIG.  66a. 

required,  but  in  practice  this  cock  is  generally  opened  wider  than  is  proper.  Claude 
recommends  that  the  carbon  monoxide  separated  from  the  water  gas  by  partial 
liquefaction  be  subjected  to  chemical  treatment  to  produce  an  approximately  equal 
volume  of  hydrogen,  this  hydrogen  to  be  added  to  further  quantities  of  water  gas 

*  Chemie  der  Case,  Brahmer  (1911),  97. 
t  J.  S.C.I.,  1911,  746. 

j  See  also  Frank,  U.  S.  Patent  873,853,  Deo.  17,  1907. 

§U.  S.  Patent  No.    1,135,355,  April  13,   1915;    French  Patent  No.  453,187;    see  also 
U.  S.  Patent  No.  1,212,455,  Jan.  16,  1917. 
||  French  Patent  No.  329,839. 


LIQUEFACTION  469 

to  be  treated.  He  makes  use  of  the  reaction  between  carbon  monoxide  and 
heated  calcium  hydrate,  affording  a  volume  of  hydrogen  gas  resulting  from  this 
step,  which  is  approximately  equal  to  the  volume  of  carbon  monoxide  gas  used. 
(See  page  4J">.) 

In  carrying  out  the  process  of  partial  liquefaction,  it  is  necessary  to  compress  not 
merely  the  water  gas  but  the  mixture  of  water  gas  and  the  hydrogen  obtained  as 
an  equivalent  of  the  carbon  monoxide;  the  ratio  of  the  volumes  of  the  gases  in  the 
two  cases  being  about  one  to  one  and  a  half.  The  nitrogen  that  the  water  gas  always 
contains  in  greater  or  smaller  proportions  accumulates  slowly.  As  soon  as  this 
nitrogen  attains  too  great  a  proportion,  it  should  be  removed. 

The  water  gas  to  be  treated  passes  through  a  pipe  W  (Fig.  66a)  to  the  compressor 
X  and  thence  to  a  cooling  coil  7,  when  it  passes  to  two  temperature  exchangers 
A  A.  From  these  exchangers  the  compressed  and  cooled  water  gas  passes  upward 
through  the  tubes  of  a  carbon  monoxide  separator  EC.  The  lower  ends  of  the  tubes 
are  surrounded  by  the  liquid  carbon  monoxide  collected  in  a  chamber  B'  under 
pressure  and  discharged  into  the  part  B  under  atmospheric  or  less  pressure;  the 
upper  ends  of  the  tubes  are  surrounded  by  the  hydrogen  resulting  from  the  separation 
and  expanded  in  an  expansion  engine  D.  The  hydrogen  circulated  in  the  part  C 
of  the  separator  passes  through  one  of  the  exchangers  A  and  thence  escapes  by  a 
pipe  H,  and  the  vaporized  carbon  monoxide  from  the  part  B  of  the  separator  passes 
through  the  other  exchanger  and  escapes  by  a  pipe  CO.  This  carbon  monoxide 
then  passes  into  a  chamber  E  where  the  reaction  between  the  carbon  monoxide  and 
calcium  hydrate  takes  place,  and  the  resultant  hydrogen  passes  to  the  pipe  W  to 
mix  with  the  incoming  water  gas.* 

In  a  description  of  a  process  of  L'Air  Liquide  f  it  is  suggested  that  in  order  to 
obtain  pure  hydrogen  by  the  partial  liquefaction  of  water  gas,  the  greater  part  of 
the  carbon  monoxide  be  liquefied  by  the  cold  produced  by  the  expansion  of  the  lique- 
fied carbon  monoxide  from  a  previous  charge.  The  last  traces  of  carbon  monoxide 
remaining  with  the  hydrogen  are  liquefied  either  by  the  cold  produced  by  the  expan- 
sion of  the  whole  or  a  portion  of  the  separated  compressed  hydrogen,  or  by  the  evap- 
oration of  liquefied  carbon  monoxide  containing  dissolved  hydrogen.  J 

The  Badische  Company  §  have  the  following  method  of  separating 
hydrogen  from  a  gaseous  mixture. 

If  water  gas  or  similar  gaseous  mixture  be  compressed  and  then  allowed  to  expand, 
the  lowering  of  temperature  produced  is  not  sufficient  to  liquefy  the  constituents 
of  the  gas.  The  invention  consists  in  adding  carbon  monoxide  or  nitrogen  to  the 
gas,  before  compression,  in  such  proportion  that  the  lowering  of  temperature  pro- 
duced on  expansion  is  sufficient  to  liquefy  the  major  portion  or  all  of  the  con- 
stituents other  than  hydrogen.  The  enrichment  of  gas  in  carbon  monoxide  or 
nitrogen  may  be  effected  by  modification  of  the  method  of  preparation  or  by  adding 
a  suitable  gas  to  the  gaseous  mixture  containing  hydrogen.  When  the  process  is 
once  in  operation  it  is  only  necessary  to  add  a  certain  quantity  of  the  constituents 

*  See  also  French  Patent  No.  469,854,  May  29,  1913;  British  Patent  No.  13,160,  1913; 
Norwegian  Patent  No.  28,254,  Oct.  8,  1917;  Chem.  Abs.,  1918,  520. 

t  Soc.  Anon,  pour  1'Etude  et  1'Exploit.  des.  Proc.  G.  Claude. 

t  French  Patents  No.  457,297,  Feb.  4,  1914,  and  475,346,  Feb.  10,  1914;  J.  S.  C.  I., 
1916,  31. 

§  German  Patent  No.  285,703,  Feb.  18,  1913;  J.  S.  C.  I.,  1915,  1133. 


470  THE  HYDROGENATION  OF  OILS 

(carbon  monoxide,  nitrogen)  which  are  liquefied,  to  the  gas  under  treatment  in 
order  to  obtain  the  desired  results. 

Mewes  *  describes  a  process  of  liquefying  and  separating  the  constituents  of  air 
and  like  gaseous  mixtures. 

The  Linde  process  for  separating  hydrogen  from  water  gas  by  fractional  lique- 
faction, the  use  of  hydrogen  in  fat  hardening  and  the  manufacture  of  synthetic 
ammonia  are  discussed  in  Seifenfabrikant,  1914,  4. 

*  British  Patent  No.  9,944,  Apr.  28,  1913;   Chem.  Aba.,  8,  1860. 


CHAPTER  XXII 
HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS 

When  methane  is  heated  to  1200°  to  1300°  C.  dissociation  occurs 
and  lamp-black  and  hydrogen  are  produced.  Acetylene  is  decom- 
posed at  a  much  lower  temperature.  In  general,  when  subjected  to 
sufficient  heat  hydrocarbons  break  down  into  their  elements.  This 
fact  has  been  made  use  of  for  the  production  of  hydrogen  by  decom- 
posing various  hydrocarbons  and  particularly  heavy  oils.  Among  the 
proposals  put  forward  up  to  the  present  time  are  some  which  relate  to 
the  splitting  of  acetylene  or  natural  gas  by  passage  through  the  heat 
zone  of  an  electric  arc  and  separation  of  the  hydrogen  from  the  lamp- 
black or  other  carbonaceous  material  which  is  formed.  The  gas  may 
be  under  pressure  to  render  the  decomposition  more  effective. 

Pictet  accomplishes  this  decomposition  by  treatment  of  the  gas  in 
heated  tubes,*  as,  for  instance,  an  endothermic  hydrocarbon,  such  as 
acetylene,  is  passed  through  a  tube,  the  front  portion  of  which  is 
heated  to  about  500°  C.,  at  which  temperature  the  gas  dissociates  into 
its  elements  with  the  evolution  of  a  large  quantity  of  heat.  The  latter 
raises  the  temperature  of  the  tube  sufficiently  to  dissociate  fresh 
quantities  of  acetylene  without  the  further  application  of  external 
heat.  The  rear  portion  of  the  tube  is  surrounded  by  a  refrigerating 
appliance,  and  the  products  of  decomposition,  hydrogen  and  lamp- 
black, are  passed  into  a  suitable  apparatus  for  their  separation.  In 
the  same  way  exothermic  hydrocarbons,  such  as  petroleum  vapors, 
mixed  with  steam  may  be  decomposed  with  the  formation  of  hydrogen 
and  carbon  monoxide;  in  this  case  the  combination  of  nascent  carbon 
and  oxygen  supplies  a  portion  of  the  heat  required  by  the  reaction, 
the  balance  which  is  required  to  dissociate  steam  and  hydrocarbon 
being  supplied  by  external  heating.  By  admitting  a  regulated  quan- 
tity of  oxygen,  -the  combination  of  the  latter  with  nascent  carbon  may 
be  made  to  provide  all  the  heat  required  by  the  reaction,  it  being  then 
only  necessary  to  heat  the  hydrocarbons  initially  to  their  temperature 
of  dissociation.  The  apparatus  may  conveniently  consist  of  a  steel, 
iron  or  porcelain  tube,  one  portion  of  which  is  heated  by  means  of  a  gas 
furnace,  and  the  other  cooled  by  water,  or  by  a  liquid  hydrocarbon, 

*  French  Patent  421,838,  Oct.  26,  1910. 
471 


472 


THE  HYDROGENATION  OF  OILS 


the  vapors  of  which  are  afterwards  admitted  to  the  tube  for  their  dis- 
sociation. The  tube  is  provided  with  the  conduits  necessary  for  the 
admission  of  the  raw  materials  and  for  the  withdrawal  of  the  products 
of  dissociation,  these  conduits  being  preferably  composed  of  "  pure 
iron  "  covered  with  nickel;  the  lamp-black  is  separated  by  washing 
or  by  means  of  filters. 

In  a  modification  of  the  foregoing  Pictet  (British  Patent  14,703,  June  21,  1911) 
operates  in  such  a  way  that  the  carbon,  instead  of  being  deposited  in  the  form  of 
soot,  is  converted  into  carbon  monoxide  by  interaction  with  water  vapor.  External 

heat  (39.36  units  for  every  18  grams  of 
water)  is  applied  for  decomposing  the 
water  vapor,  in  addition  to  that  required 
to  decompose  the  hydrocarbon  vapors, 
for  which  the  temperature  is  raised  sub- 
stantially to  the  melting  point  of  iron. 
Water  and  hydrocarbon  are  fed,  for  ex- 
ample, into  an  iron  tube,  which  is  of 
sufficient  length  (say  3  to  4  meters)  to 
enable  the  supplementary  heat  to  be 
imparted  without  damage,  and  these 
being  vaporized  on  entry,  react  in  the 
further  end  of  the  tube,  which  is  the 
more  strongly  heated;  the  gas  produced 
is  then  cooled  and  passes  through  a  filter 
to  a  gas  holder,  there  being  a  soot 
chamber  and  also  arrangements  for  the 
removal  of  soot  from  the  tube  and  filter. 
Ten  liters  of  petroleum,  mixed  with  3  to 
5.5  liters  of  water,  may  be  thus  decom- 
posed per  hour,  in  the  apparatus  de- 
scribed, the  mixture  furnishing  approx- 
imately 3000  liters  of  gas  for  every  liter 
of  hydrocarbon,  with  a  calorific  value  of 
3000  to  3600  heat  units  per  cubic  meter. 
By  regulating  the  supply  of  water,  any 

FIG.  67.  desired  proportion  of  carbon  can  be  con- 

verted into  carbon  monoxide. 

In  preparing  hydrogen  from  crude  petroleum  or  petroleum  tar  oils  (British  Patent 
13,397,  June  3,  1911)  the  vapors  are  heated  in  such  a  manner  that  18.1  calories  are 
supplied  to  16  grams  of  gas,  with  a  tube  temperature  of  1200°  to  1350°  C. 

Another  process  worked  out  by  the  Carbonium  Company  in  Germany 
employs  acetylene  gas  which  is  compressed  to  two  atmospheres  and 
exploded  by  an  electric  spark.* 

C2H2  =  C2  +  H2. 

The  acetylene  thereby  dissociates  into  the  elements  carbon  and  hydro- 
*  Met.  and  Chem.  Eng.  (1911),  157. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS       473 

gen.  The  carbon  deposits  in  the  form  of  lamp-black.  The  hydrogen 
is  passed  through  large  washer  and  stored.  Its  degree  of  purity  is  ex- 
ceptionally high.  For  each  cubic  meter  of  hydrogen  produced  about 
one  kilo  of  lamp-black  is  formed.  A  condition  for  getting  the  hydrogen 
cheaply  by  this  method  is  that  there  is  a  market  for  the  lamp-black. 

Wachtolf  *  compresses  the  acetylene  to  about  4  to  6  atmospheres 
and  explodes  electrically.  In  Fig.  67  the  explosion  chamber  is  shown 
on  the  left  and  a  lamp-black  collector  on  the  right.  The  explosion 
chamber  is  provided  with  a  rotary  scraper  to  remove  lamp-black 
adhering  to  the  walls. f 

Geisenberger  J  generates  hydrogen  alone  or  mixed  with  carbon 
monoxide  or.  carbon  dioxide,  by  the  action  of  heat  alone  or  of  heat  and 
steam,  on  light  hydrocarbons,  such  as  benzine,  or  on  other  materials 
containing  hydrogen  and  carbon,  e.g.,  bitumen,  shale,  beeswax,  tur- 
pentine, etc.  The  organic  substance  is  heated  in  a  retort,  to  which 
steam  may  be  admitted,  to  its  point  of  decomposition.  The  hydro- 
gen is  separated  from  the  other  gases  in  the  mixture  obtained,  either 
by  physical  means,  depending  on  the  differences  in  density,  or  by 
chemical  means,  such  as  absorbing  the  carbon  dioxide  by  means  of 
sodium  carbonate  or  hydroxide  solution. 

Rincker  and  Wolter  §  make  use  of  two  generators,  somewhat  re- 
sembling those  used  in  making  water  gas,  for  the  decomposition  of 
oils  and  tars.  These  generators  are  arranged  side  by  side  and  charged 
with  coke.  After  they  have  been  raised  to  incandescence  by  a  blast 
of  air,  a  charge  of  tar  is  introduced  into  one  of  them  and  is  partly 
transformed  into  gas  by  the  glowing  fuel.  The  gas  formed  escapes 
by  its  own  expansion.  A  current  of  air  is  then  introduced  which 
carries  forward  the  remaining  vapors  of  tar  into  the  second  generator 
where  they  are  converted  into  a  permanent  gas.  At  the  same  time 
the  blast  of  air  raises  the  contents  of  the  first  generator  to  incandescence 
again,  and  the  process  is  reversed  by  introducing  the  tar  into  the 
second  generator  and  repeating  the  operations  in  the  reverse  direction. 

In  a  modified  form  of  the  apparatus  ||  the  two  generators  are  ar- 
ranged one  above  the  other  and  are  charged  with  coke.  The  coke  in 
the  lower  generator  is  ignited  and  then  brought  to  incandescence  by 
a  blast  of  air  which  has  been  preheated  by  being  caused  to  pass  through 
a  jacket  surrounding  the  upper  generator.  The  fuel  in  the  latter  is 

*  German  Patent  194,301. 

t  Decomposition  of  hydrocarbons  under  pressure  is  described  by  Bosch,  German 
Patent  268,291,  July  14,  1911;  Chem.  Zeit.  Rep.  (1914),  32. 
t  French  Patent  361,492,  Dec.  21,  1905. 
§  French  Patent  391,868,  May  11,  1908. 
||  French  Patent  391,867,  May  11,  1908. 


474 


THE  HYDROGENATION  OF  OILS 


also  ignited  and  then  raised  to  incandescence  by  natural  draught. 
The  products  of  combustion  are  allowed  to  escape  to  the  chimney. 
When  the  fuel  is  glowing  brightly,  the  air  supply  is  cut  off  and  a  charge 
of  oil  is  introduced  into  the  lower  generator  through  pipes  in  the  top. 
The  oil  passes  over  the  glowing  fuel  and  is  partially  converted  into 
permanent  gas  which  escapes  through  a  pipe  in  the  side  by  its  own 


FIG.  68. 

expansion.  The  blast  of  air  is  then  again  turned  on,  whereby  the 
vapors  of  oil  left  in  the  lower  generator  are  blown  into  the  upper  one, 
where  they  are  gasified  and  fixed  during  their  passage  through  the 
glowing  fuel.  The  lower  generator  is  at  the  same  time  again  raised  to 
incandescence  and  the  process  is  repeated.* 

*  Apparatus  for  the  production  of  hydrogen  by  the  decomposition  of  the  vapors 
of  oil  or  tar  by  exposure  to  a  high  temperature  is  the  basis  of  a  patent  to  the  Berlin- 
Anhaltische  Maschinenbau-Aktien-Gesellschaft,  Berlin,  German  Patent  267,944, 
Jan.  28,  1913;  Chem.  Zeit.  Rep.  (1914),  31. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS      475 

Equipment  for  the  Rincker-Wolter  system  is  manufactured  by  the  Hollandsche 
Residugas-Maatschappij  of  Rotterdam.  The  gas-making  plant  consists  of  twin 
generators,  Fig.  68,  lined  with  firebrick  and  provided  with  grate  bars  and  clinkering 
doors,  in  short,  resembling  water-gas  generators  but  lacking  a  carburettor  and  super- 
heater. The  generators  are  connected  near  the  top  and  in  the  upper  part  are  lids 
for  feeding  purposes,  which  carry  sprayers  for  introduction  of  the  oil. 

Fig.  69  shows  the  operating  floor  of  one  of  these  plants.     The  generators  are 


FIG.  69. 

equipped  with  primary  and  secondary  blast  pipes,  steam  inlets  and  dust  collectors. 
Both  generators  are  charged  with  coke  and  fired.  The  generators  are  operated 
alternately  in  the  blowing-run,  the  first  generator  receiving  the  primary,  and  the 
second  generator  the  secondary,  ah-  blast.  Combustion  is  incomplete  in  the  first 
generator  and  the  producer  gas  obtained  is  led  to  the  second  generator  where  it  is 
burned  on  meeting  the  current  of  secondary  air,  thus  heating  up  the  second  generator. 
As  it  is  preferable  to  reach  nearly  equal  temperatures  in  both  generators,  the 
sequence  is  reversed  after  a  short  blowing  and  the  first  generator  becomes  second  in 
the  series.  When  both  generators  have  reached  the  proper  temperature,  the  air 
valves  are  shut  and  the  gas  run  begins.  The  temperature  of  the  fuel  bed  has  to 
be  varied  somewhat  according  to  the  nature  of  the  raw  materials.  For  hydrogen 
production  a  temperature  of  about  1200°  C.  is  required.  Too  low  a  temperature 
gives  so  impure  a  gas  that  subsequent  purification  of  the  hydrogen  is  rendered  costly. 
At  the  end  of  the  blowing-run  oil  is  sprayed  for  several  minutes  on  the  hot  coke  and 
gasification  takes  place.  Immediately  after  this  the  sprayer  is  cleaned  by  blowing 
steam  through  it.  The  gas  formed  by  decomposition  of  the  oil  passes  to  a  seal  and 
from  there  to  scrubbers  and  purifiers. 


476  THE  HYDROGENATION  OF  OILS 

Fig.  70  shows  the  gas  outlets  and  seal.  The  residue  of  gas  in  the 
generators  is  expelled  by  steam.  Lamp-black  is  deposited  in  the 
generators  and  is  consumed  in  the  next  run.  Fig.  71  shows  the  gener- 
ators of  a  plant  at  Utrecht. 

In  a  well-handled  run  gas  of  the  following  composition  is  said  to  be 
obtained : 

Per  cent 

H 96 

N 1.3 

CO 2.7 

And  by  passing  this  gas  over  heated  soda-lime  a  gas  has  been  secured 
analyzing: 

Per  cent 

H 98.4 

N 1.2 

CO* 0.4 

To  avoid  difficulties  from  clinkering  of  the  ash  of  the  fuel,  the  author 
has  suggested  the  addition  of  a  small  proportion  of  lime  to  the  charge  of 
coke,  so  as  to  flux  the  ash  and  thus  to  enable  the  maintenance  of  the 
requisite  high  temperature  in  the  fuel  bed.f 

A  method  of  preparing  hydrogen  is  proposed  by  the  Badische  Anilin 
und  Soda  Fabrik  {  according  to  which  a  mixture  of  hydrocarbons  and 
steam  is  passed  over  an  inactive,  refractory  oxide,  such  as  magnesia, 
coated  with  nickel  or  nickel  oxide,  at  a  temperature  of  800°  to  1000°. 
The  resulting  gaseous  mixture  is  freed  from  carbon  monoxide  and 
dioxide,  leaving  substantially  pure  hydrogen. 

Efforts  to  secure  hydrogen  from  illuminating  gas  have  met  with  a 
considerable  measure  of  success.  By  the  process  of  Oechelhauser 
hydrogen  of  about  80  per  cent  purity  is  obtained.  A  gas  of  much 
higher  hydrogen  content  has  been  produced  by  the  Berlin- Anhaltischen 
Maschinenbau  —A.—G.  which  is  based  on  investigations  made  by 
Bunte.  The  illuminating  gas  is  first  freed  of  carbon  dioxide  and  is 
then  conducted  over  white-hot  coke  which  decomposes  the  hydro- 
carbons and  yields  a  gas  mixture  consisting  almost  entirely  of  hydro- 
gen, carbon  monoxide  and  nitrogen.  The  carbon  monoxide  is  removed 

*  Sanders  (Zeitsch.f.angew.  Chem.  (1912),  2404)  states  that  the  cost  of  hydrogen 
by  the  Rincker-Wolter  system  is  10.5  to  14  pfennig  per  cubic  meter.  In  a  private 
communication  to  the  author,  the  manufacturers  advise  the  cost  of  the  smallest 
equipment  they  make,  having  a  capacity  of  3500  cubic  feet  of  hydrogen  per  hour,  is 
$2575  plus  erecting  expenses.  With  oil  at  about  4  cents  per  gallon  the  hydrogen  is 
estimated  to  cost  about  $1.75  per  thousand  cubic  feet. 

t  Ellis,  U.  S.  Patent,  1,092,903,  April  14,  1914. 

t  J.  S.  C.  I.,  1914,  313. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS      477 


FIG.  70. 


FIG.  71, 


478 


THE  HYDROGENATION  OF  OILS 


by  treatment  with  soda  lime  and  the  gas  then  consists  largely  of  hydro- 
gen with  only  nitrogen  as  an  impurity.  The  specific  gravity  is  0.085 
to  0.097  and  the  gas  has  been  found  to  be  well  adapted  for  most 
technical  purposes.  The  process  can  be  put  in  operation  at  any  gas 
works  equipped  with  a  water-gas  plant  and  the  installation  is  not 
very  costly.* 

Pictet,  f  in  the  production  of  a  gas  of  high  heating  value,  heats  crude 
petroleum,  tar  oil  or  similar  hydrocarbons  in  tubes  to  such  a  tempera- 
ture (e.g.,  900°  to  1200°),  that  not  all  the  hydrogen  splits  off  as  such, 
but  appears  in  the  end  product  as  methane.  The  hydrocarbons  to  be 
broken  down  may  be  employed  mixed  with  gases  of  less  heat  value, 
such  as  hydrogen,  water  gas,  etc. 

The  addition  of  hydrogen  and  oxygen  can  be  so  proportioned  that  carbon  monox- 
ide and  pure  hydrogen  alone  result.  {  Pictet  produces  carbon  monoxide  and  hydro- 
gen §  by  simultaneously  admitting  steam,  oxygen  and  petroleum  oil  (in  vaporized 


FIG.  71a. 

form)  into  a  horizontal  pipe  heated  externally  in  a  furnace  to  a  temperature  suf- 
ficiently high  to  decompose  the  steam  and  hydrocarbon.  A  temperature  of  1300° 
to  1500°  C.  may  be  employed.  A  mixture  of  hydrogen  and  carbon  monoxide  is 
obtained. 

Frank  1 1  passes  purified  natural  gas  through  a  furnace  filled  with  incandescent 
coke  or  refractory  material  thereby  producing  hydrogen.  Natural  gas  is  first  freed 
of  hydrogen  sulphide  by  passage  through  a  purifier  which  contains  an  iron  oxide, 
such  as  limonite.  Thereupon  the  gas  is  subjected  to  a  temperature  of  at  least 
1200°  C.  The  decomposition  of  the  gas  begins  at  a  temperature  of  about  800°  C., 
while  the  gas  is  completely  split  into  carbon  and  hydrogen  when  the  highest  tempera- 

*  Sander,  Zeitsch.  f.  angew.  Cheniie  (1912),  2406. 

t  German  Patent  No.  277,115,  Feb.  13,  1913.  Addition  to  No.  257,715;  Chem.  Abs., 
1915,  712;  German  Patent  No.  289,065,  Dec.  7,  1912.  See  also  Canadian  Patent,  No. 
184,460,  May  21,  1918. 

J  U.  S.  Patent  No.  1,134,416,  Apr.  6,  1915;   Chem.  Abs.,  1915,  1374. 

§  U.  S.  Patent  No.  1,228,818,  June  5,  1917. 

||  U.  S.  Patent  No.  1,107,926,  Aug.  18,  1914;  Chem.  Abs.,  19-14,  3359. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS  479 

ture,  exceeding  1200°  C.,  is  attained.  Frank  notes  that  at  this  temperature  the 
higher  hydrocarbons  also  are  decomposed  into  carbon  and  hydrogen.  The  apparatus 
is  shown  in  Fig.  71a. 

Rose  *  prepares  gas  containing  as  high  as  98  per  cent  hydrogen  by 
passing  natural  gas  or  oil  over  refractory  surfaces  heated  to  1650°  C. 

The  production  of  hydrogen  and  soot  by  the  pyrogenic  breaking  down  of  light 
hydrocarbons,  especially  natural  gas,  by  contact  with  highly-heated  refractory 
surfaces,  against  which  the  gas  under  treatment  is  directed  in  a  number  of  finely- 
divided  currents  is  described  by  Herman,  f  With  the  exclusion  of  air,  the  baking 
and  graphitizing  of  the  soot  on  the  surfaces  may  be  prevented  by  a  uniform  heating 
of  the  surfaces  serving  for  the  decomposition  and  a  careful  removal  of  the  soot 
from  the  heated  surfaces  after  its  formation.  The  hydrogen  is  drawn  off  and  cooled 
immediately. 

Mittasch  and  Schneider  {  pass  hydrocarbons  and  steam  over  a  nickel 
catalyzer  distributed  on  a  fireproof  carrier  at  a  temperature  of  some- 
what above  700°  C.  and  produce  hydrogen  and  carbon  monoxide  or 
carbon  dioxide.  § 

They  state  that  the  conversion  of  hydrocarbons  and  steam  into  hydrogen  and 
carbon  monoxide  or  carbon  dioxide  can  be  carried  out  rapidly  and  completely  by 
employing  a  nickel  catalytic  agent  distributed  on  a  fireproof  carrier  and  by  working 
at  a  temperature  above  that  of  dark  redness,  that  is  to  say  above  700°  C.  Mittasch 
and  Schneider  observe  that  during  the  reaction  it  is  possible  that  the  nickel  is  con- 
verted into  an  oxide  of  nickel;  or  vice  versa,  it  is  also  possible  that  the  oxide  or  other 
compound,  of  nickel  is  reduced  to  the  metallic  form  or  to  a  compound  containing 
carbon,  so  that  it  is  equivalent  whether  metallic  nickel  or  nickel  oxide  or  other  suit- 
able nickel  compound  be  taken  at  the  commencement  of  the  reaction.  Such  car- 
riers are  employed  as  do  not  react  with  nickel  oxide  under  the  conditions  obtaining 
during  the  reaction,  since  the  contact  mass,  it  is  claimed,  then  retains  its  activity 
even  after  being  employed  for  a  long  time. 

When  working  according  to  the  present  invention,  a  gas  mixture  free  from  or 
containing  only  small  quantities  of  hydrocarbons  results  and  after  removal  of  the 
carbon  monoxide  and  carbon  dioxide  gives  rise  to  hydrogen  which  Mittasch  and 
Schneider  note  is  suitable  for  the  catalytic  production  of  ammonia,  or  for  reducing 
fats. 

The  process  is  carried  out  in  upright  furnaces  or  tubes  lined  with  fireproof  material. 
The  necessary  heat  can  be  applied  internally,  by  burning  hydrocarbons  in  the  reac- 
tion space  and  this  heating  can  be  carried  on  before  or  during  the  actual  production 
of  hydrogen.  It  is  particularly  advantageous  to  pass  alternately  mixtures  of  hydro- 
carbon or  other  fuel  and  air,  and  hydrocarbon  and  steam,  into  the  reaction  space 
since  by  this  means  it  is  easy  to  maintain  the  requisite  temperature.  The  heat 
contained  in  the  gases  leaving  the  reaction  space  can  be  used  to  preheat  the  gas 

*  U.  S.  Patent  No.  1,254,360,  Jan.  22,  1918. 
t  German  Patent  No.  290,883,  Oct.  23,  JL914. 
%  U.  S.  Patent  No.  1,128,804,  Feb.  16,  1915. 

§  See  French  Patent  No.  463,114,  of  1913;  J.  S.  C.  I.,  1914,  313;  also  British  Patent 
No.  12,978,  June  4,  1913. 


480  THE  HYDROGENATIOX  OF  OILS 

mixture  about  to  enter  the  furnace.  The  gas  mixture  obtained,  in  so  far  as  it  con- 
tains carbon  monoxide,  if  necessary  after  adding  a  further  quantity  of  steam,  can  be 
passed  over  a  contact  agent,  in  order  to  convert  the  carbon  monoxide  into  carbon 
dioxide. 

The  following  procedure  will  serve  to  illustrate  the  process:  Magnesia  in  the 
form  of  lumps  is  burnt  at  a  high  temperature.  The  lumps  are  soaked  with  a  solu- 
tion of  nickel  nitrate  so  that  the  magnesia  contains  from  about  2  to  5  per  cent  of 
nickel,  and  then,  after  heating  to  decompose  the  nitrate,  the  product  is  placed  in  a 
contact  furnace  and  a  mixture  containing  methane  and  steam  is  passed  over  it  at 
from  800°  to  1000°  C.  The  reaction  takes  place  rapidly  and  the  activity  of  the 
catalytic  agent  does  not  diminish.  Another  method  of  producing  a  catalyst  of  this 
character,  recommended  by  Mittasch  and  Schneider  consists  in  precipitating  metallic 
nickel  on  a  carrier  by  the  decomposition  of  nickel  carbonyl. 

Instead  of  gaseous  hydrocarbons,  either  liquid  or  solid  hydrocarbons  can  be  used, 
in  which  case  the  latter  are  first  vaporized  or  are  injected  directly  into  the  reaction 
space,  or  the  pipes  leading  to  the  reaction  space.  Further,  mixtures  containing 
hydrocarbons  can  be  employed  such  as  coal  gas.  The  nickel  also  can  be  used  in 
admixture  with  other  metals  or  metallic  oxides. 

Brownlee  and  Uhlinger  *  employ  a  method  of  obtaining  carbon 
monoxide,  hydrogen  and  nitrogen  from  the  products  of  combustion  of 
internal  combustion  engines. 

Natural  gas,  coal  gas,  or  other  suitable  gaseous,  liquid  or  solid  carbonaceous  sub- 
stance, is  mixed  with  an  amount  of  air  not  sufficient  for  complete  combustion,  and 
the  mixture  is  exploded  in  the  cylinder  of  an  internal  combustion  engine.  The 
mixture  is  so  regulated  that  the  proportion  of  air  is  such  as  to  yield  the  largest 
practicable  quantities  of  carbon  monoxide  and  hydrogen.  For  example,  if  natural 
gas  is  used,  a  mixture  of  approximately  1  volume  of  gas  to  65  volumes  of  air  is  prefer- 
ably employed  with  a  compression  before  explosion  of  70  to  80  Ib.  Under  these 
conditions  considerable  power  is  produced  and  at  the  time  good  yields  of  carbon 
monoxide  and  hydrogen  are  obtained.  The  mixture  of  water  vapor,  carbon  dioxide, 
carbon  monoxide,  hydrogen  and  nitrogen  resulting  after  the  combustion  or  explosion 
is  cooled  to  remove  the  moisture,  then  compressed,  and  the  carbon  dioxide,  carbon 
monoxide  and  nitrogen  liquefied  in  turn,  thus  leaving  hydrogen  in  the  gaseous  state, 
but  highly  compressed.  Instead  of  compressing  and  liquefying  the  carbon  dioxide, 
etc.,  after  the  removal  of  moisture  by  cooling,  this  gas  may  be  absorbed  with  suit- 
able absorbents,  as  calcium  hydroxide,  and  the  carbon  monoxide  may  be  with- 
drawn by  ammoniacal  cuprous  chloride  solution,  leaving  the  nitrogen  and  hydrogen 
to  be  separated  by  compression  and  liquefaction  of  the  nitrogen.  In  place  of  air, 
nearly  pure  oxygen  may  be  used.f  A  mixture  of  equal  volumes  of  natural  gas  and 
oxygen  may  be  employed  under  a  compression  of  70  to  80  Ib.  From  1000  cu.  ft. 
of  Pennsylvania  natural  gas  1300  to  1350  cu.  ft.  of  hydrogen  will  be  obtained. 

Brownlee  and  Uhlinger  {  describe  a  process  of  producing  hydrogen 
and  carbon  black  which  consists  in  passing  hydrocarbons,  at  a  pressure 

*U.  S.  Patent  No.  1,107,581,  Aug.  18,  1914». 
t  U.  S.  Patent  No.  1,107,582. 

JU.  S.  Patent  No.  1,168,931,  Jan.  18,  1916,  No.  1,265,043,  May  7,  1918  and 
1,276,487,  Aug.  20,  1918.  See  also  1,276,385  to  McCourt  and  Ellis. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS  481 

above  atmospheric,  over  a  highly  heated  mass  of  refractory  material 
which  is  free  from  easily  reducible  metallic  oxides.  The  refractory 
material  is  first  heated  to  about  1400°  C.  and  then  gas  or  oil  vapors 
passed  in  from  the  top.  The  carbon  is  collected  in  a  chamber  and 
removed  as  collected  by  means  of  a  screw  conveyer.  The  hydrogen  is 
purified  if  nece  ,sary  and  passed  into  a  gas  heater.  Any  carbon  which 
may  be  deposited  on  the  refractory  material  will  be  burned  off  on  reheat- 
ing for  further  decomposition.  Fig.  716  shows  a  diagram  of  the  appa- 
ratus. 

Bacon,  Brooks  and  Clark  *  have  devised  a  process  for  obtaining 
carbon  black,  and  practically  pure  hydrogen,  by  the  decomposition  of 


FIG.  716. 

hydrocarbons,  the  conditions  of  working  being  such  as  to  insure  a  satis- 
factory yield  of  both  products  in  a  continuous  operation.  The  apparatus 
employed  is  adapted  to  develop  and  maintain  the  high  temperatures 
required  and  withstand,  during  long-continued  use,  the  exacting  require- 
ments imposed  upon  it. 

Bacon,  Brooks  and  Clark  stc.te  that  unless  the  carbon  black  produced  as  one  of 
the  products  of  the  decomposition  is  promptly  removed  from  the  high  temperatures 
(exceeding  1200°  C.)  of  the  heating  zone  in  which  the  decomposition  is  proceeding, 
such  carbon  black  will  deteriorate  in  quality  for  commercial  uses,  losing  its  desired 
deep  black  luster,  and  becoming  materially  duller  and  grayer.  Accordingly,  the 
operation  is  conducted  so  that  the  particles  of  carbon  black  will  remain  suspended  in 
the  hydrogen,  and  are  removed  with  the  hydrogen  from  the  zone  of  decomposition. 


*U.  S.  Patent  No.  1,220,391,  Mar.  27,  1917. 
1918,  to  McCourt  and  Ellis. 


See  also  No.  1,276,385,  issued  Aug.  20, 


482 


THE  HYDROGENATION  OF  OILS 


In  Fig.  71c  is  shown  a  gas-tight  metal  shell,  having  a  gas-tight  cover.  The 
casing  is  provided  at  one  end  with  an  exit  pipe  for  the  outflow  of  the  carbon  black 
and  hydrogen,  and  has  an  opening  at  its  opposite  end  closed  by  a  removable  gas- 
tight  asbestos  board  closure.  Within  the  casing  is  a  lining  of  fire-brick  and  an  inner 
lining  of  magnesite  brick.  In  the  chamber  is  located  the  heating  element  which  is 
made  up  of  a  double  series  of  graphite  rings  cut  in  two  diametrically.  Through 


FIG.  71c. 

stuffing  boxes  of  the  face  plate  there  extend  carbon  rods,  each  of  which  is  connected 
to  the  same  terminal  of  an  electric  heating  circuit.  The  hydrocarbon  to  be  decom- 
posed is  supplied  in  a  thin  stream  through  the  inlet  pipe  on  the  left.  It  enters  the 
decomposition  zone  of  the  apparatus,  made  up  of  the  annular  walls  of  the  series  of 
graphite  rings,  which  rings  are  heated  by  an  electric  current  to  a  temperature  ex- 
ceeding 1200°  C.  and  sufficient  to  flash  and  decompose  the  hydrocarbon  into  carbon 
black  and  hydrogen.  The  temperature  of  flashing  or  decomposition,  and  the  quan- 
tity of  liquid  hydrocarbon  injected  are  so  adjusted  that  the  gas  pressure  developed 


Hydrogen  Gas 

-*f  ^ *" 
Waste  Gas- 

.      FIG,  7ld. 

shall  be  sufficient  to  sweep  the  particles  of  carbon  black  without  permitting  them 
to  settle  in  the  decomposition  zone  of  the  apparatus.  The  carbon  black  is  deposited 
in  a  settling  chamber,  and  the  hydrogen  is  carried  on  to  a  gas  holder.  The  carbon 
black  recovered  is  of  a  black  silky  luster,  and  the  hydrogen  is  substantially  pure. 

Ellis  describes  *  a  type  of  furnace  connected  to  a  checker-work 
chamber,  to  be  used  for  the  heat  decomposition  of  oils  to  yield  hydrogen. 

*  U.  S.  Patent  No.  1,092,903,  Apr.  14,  1914. 


HYDROGEN  BY  THE  DECOMPOSITION  OF  HYDROCARBONS  483 


A  bed  of  coke  in  the  furnace  is  heated  to  white  heat  and  hydrocarbon 
oil  entered  above  the  bed  where  it  is  decomposed.  The  vapors  pass 
through  the  heated  checker  work  and  are  further  decomposed.  The 
furnace  is  provided  with  air  and  steam  inlet  pipes  for  blowing  up  the 
fire  and  for  sweeping  out  contaminating  gases.  Fig.  7 Id  shows  this 
form  of  apparatus. 

By  a  modification  of  the  Rincker-Wolter  process  *  liquid  hydro- 
carbons are  converted  into  oil-gas,  on  contact  with  glowing  coal  or 
coke  in  the  customary  manner,  and  water  gas  or  other  gas  containing 
hydrogen  is  led  into  the  oil-gas  generator  with  the  object  of  converting 
the  oil  residues  into  hydrocarbons  that  can  be  gasified.  The  forma- 
tion of  tar  in  the  oil-gas  generator  is  thus  avoided.  Two  generators 
are  used,  each  serving  as  a  water-gas  generator  and  an  oil-gas  generator 
alternately,  t 

A  portable  plant  of  the  Rincker-Wolter  type,  which  may  be  used  for  military 
purposes,  is  arranged  so  compactly  that  it  may  be  mounted  on  two  ordinary  railway 
flat  cars.  The  apparatus  consists  of  two  gas  producers  in  which  hydrogen  is  made 
from  oil  which  is  sprayed  into  the  producer.  The  gas  is  then  passed  through  puri- 
fiers and  driers  to  give  hydrogen  of  the  desired  purity.  In  case  it  is  necessary  to 
compress  the  gas  a  third  car  is  necessary.  I 

Barth  §  produces  hydrogen  by  first  decomposing  oil  in  a  furnace  and 
then  further  heating  the  gas 
formed  in  a  separate  furnace 
to  produce  hydrogen.  He 
claims  for  this  method  that 
there  is  an  economical  use  of 
fuel  and  that  the  contact 
mass  in  which  the  hydrogen 
is  formed  does  not  become 
contaminated  with  carbon, 
etc. 

The  furnace  or  vaporization 
chamber  used  by  Barth,  see  Fig. 
71e,  is  constructed  of  an  iron 
jacket  which  has  a  lining  of  re- 
fractory bricks,  and  which  is  filled 
with  a  refractory  grating  or  with 
coarse  pieces  of  refractory  material.  The  gases  of  combustion  which  escape  from 
the  generator  during  the  blowing  or  reheating  period  are  passed  through  the 

*  British  Patent  No.  6,285,  Apr.  27,  1915. 
t  See  also  Canadian  Patent  No.  181,962,  Feb.  5,  1918. 
J  Scientific  American  Supp.,  Sept.  5,  1914,  155. 
§  U.  S.  Patent  No.  1,172,925,  Feb.  22,  1916. 


FIG.  7le. 


484 


THE  HYDKOGENATION  OF  OILS 


refractory  grating  of  the  vaporization  chamber.  Near  the  end  of  the  blowing 
period  the  gases  contain  a  certain  amount  of  carbonic  oxide  which  is  burnt  within 
the  vaporization  chamber  by  admitting  air  thereto.  By  this  operation  the  grating 
of  refractory  material  within  the  vaporization  chamber  accumulates  the  heat 
which  is  necessary  for  vaporizing  the  liquid  fuel  and  in  some  cases  for  partly 
decomposing  the  same.  Finally  the  air  supply  is  shut  off,  and  the  vaporized  oil  or 
other  fuel  is  passed  into  the  vaporization  chamber  through  several  nozzles  and 
vaporized  therein.  The  vapors  are  passed  through  the  glowing  charge  of  coke 
within  the  generator,  where  they  are  decomposed  in  such  a  way  as  to  split  off  carbon 
and  to  produce  either  an  illuminating  and  heating  gas  (if  the  process  is  carried  out 
at  a  temperature  of  about  1000°  C).,  or  hydrogen  (if  the  process  is  carried  out  at  a 
higher  temperature) .  The  vapors  of  oil  or  other  fuel  are  alternately  passed  through 
the  generator  in  opposite  directions,  that  is  alternately  from  above  downward  and 
from  below  upward.  Thereby  the  heat  which  has  been  accumulated  within  the 
generator  is  uniformly  consumed,  and  the  lower  part  of  the  generator  which,  during 
the  blowing  period,  is  subject  to  the  highest  strain  is  not  brought  to  an  excessive 
temperature. 

A  process  of  producing  hydrogen  gas  or  gas  containing  this  constituent  is  proposed 
by  Lowe  *  which  involves  heating  a  bed  of  solid  fuel  to  incandescence,  in  passing  into 
the  ignited  mass  a  quantity  of  petroleum  oil  which  breaks  down  into  hydrogen  and 
carbon.  The  hydrogen  is  removed  and  the  deposit  of  carbon  is  subjected  to  com- 
bustion with  an  amount  of  air  sufficient  only  to  consume  part  of  the  carbon 
which  has  been  deposited.  Then  further  quantities  of  petroleum  oil  are  injected 
into  the  fuel  mass.t 

Snelling,|  employs  carbon  compounds  which  are  capable  of  dis- 
sociation by  heat  in  a  reversible  manner,  with 
the  liberation  of  hydrogen.  These  compounds 
are  heated  in  a  closed  chamber  or  tube  with 
walls  more  permeable  by  hydrogen  than  by 
other  substances  present,  and  the  hydrogen 
formed  is  thus  withdrawn  during  the  reaction.  § 

An  apparatus  for  producing  hydrogen  from  natural 
gas,  crude  petroleum  or  garbage  grease  designed  by 
Brunner  1 1  employs  a  series  of  vertical  stand  pipes 
alternately  connected  at  top  and  bottom  and  internally 
sprayed  with  water  to  remove  carbon  and  other  im- 
purities. The  water  is  finally  discharged  through  a  liquid 
seal  at  the  bottom  of  each  pipe.  (See  Fig.  71/.)  The 


FIG.  71/. 
organic  material  is  heated  in  an  adjacent  furnace  (not  shown). 

*  U.  S.  Patent  No.  1,174,511,  March  7,  1916. 
t  See  also  Frasch,  U.  S.  Patent  No.  1,118,899,  Nov.  24,  1914. 
J  J.  S   C.  I.,  1915,  249;   U.  S.  Patent  No.  1,124,347,  Jan.  12,  1915. 
§  See  also  O.  P.  &  D.  Reporter,  Apr.  5,  1915,  34. 

II  U.  S.  Patent  No.  1,246,867,  Nov.  20,  1917;  Chem.  Abs.,  1918,  297;  J.  S.  C.  I.,  1918, 
30A. 


CHAPTER   XXIII 

HYDROGEN  BY  THE  ACTION   OF   STEAM   ON   HEATED 

METALS 

• 

A  large  number  of  proposals  for  making  hydrogen  exist  which  are 
based  on  a  very  old  reaction,  namely,  the  passage  of  steam  over  red 
hot  iron  in  a  finely-divided  state.     The  main  reaction  which  occurs  is 
3  Fe  +  4  H20  =  Fe304  +  4  H2. 

On  the  large  scale  it  becomes  necessary  to  regenerate  the  iron  material ; 
which  is  effected  by  reduction,  usually  with  water  gas.  With  an  im- 
pure gas  slagging  difficulties  arise.  Giffard  found  that  the  charge  of 
iron  soon  became  inefficient  because  the  sulfur  in  the  gas  formed  on 
the  iron  particles  a  resistant  coating  of  iron  sulfide,  which  also  acted 
as  a  flux  and  caused  the  iron  material  to  sinter  into  a  coherent  mass. 
Hence  prior  purification  of  the  reducing  gas  was  found  necessary  for 
satisfactory  operation.  Apart  from  the  sintering  effect  of  sulfur  on 
the  iron  material,  the  water  gas  should  be  freed  from  this  element  as 
otherwise  the  hydrogen  would  take  up  sulfur  and  poison  the  cata- 
lyzer. For  each  cubic  foot  of  hydrogen  produced,  about  three  cubic 
feet  of  water  gas  are  required.  This  requires  the  purification  of  three 
volumes  of  water  gas  for  one  volume  of  hydrogen. 

Some  of  the  processes  described  have  had  little  or  no  commercial 
success,  but  are  included  because  they  involve  certain  features  which 
are  suggestive  or  instructive. 

Lewes  *  prepared  hydrogen  in  the  following  manner: 

A  retort,  partly  filled  with  iron  borings,  or  with  a  mixture  of  iron  and  carbonaceous 
material,  or  with  asbestos  containing  iron  in  a  very  fine  state  of  division,  is  placed 
in  the  center  of  a  gas  producer.  By  means  of  an  air  blast  the  fuel  in  the  producer 
is  raised  to  a  bright  red  heat  and  then  a  little  steam  is  admitted  together  with  the 
air.  The  gaseous  mixture  of  carbonic  oxide,  nitrogen  and  hydrogen  produced  in 
this  way  is  led  from  the  top  of  the  producer  down  through  the  retort.  As  soon  as 
the  iron  oxide  in  the  retort  is  completely  reduced,  and  the  requisite  temperature 
has  been  attained,  the  producer  gas  is  turned  off  and  steam,  previously  heated  in 
the  producer,  is  passed  over  the  iron,  the  hydrogen  being  led  away  to  a  gasometer. 
The  process  is  then  repeated  as  described.  One  of  the  advantages  claimed  for 
this  form  of  apparatus  is  that  the  rapid  cooling  of  the  iron  during  the  decomposition 
of  the  steam  is  prevented.  Lewes  claims  (British  Patent  4134,  March  7,  1891)  the 

*  British  Patent  20,752,  Dec.  19,  1890. 
485 


486  THE  HYDROGENATION  OF  OILS 

use  of  a  mixture  of  carbonic  oxide,  nitrogen  and  hydrogen  for  the  reduction  of  oxide 
of  iron  in  the  above  process.  This  gaseous  mixture  is  regarded  as  a  better  reducing 
agent  than  carbonic  oxide,  and  is  easily  obtained.  The  finely-divided  iron  employed 
for  the  production  of  hydrogen  is  prepared  by  saturating  asbestos  or  pumice  with 
certain  iron  salts,  which  are  easily  decomposed  into  oxide  of  iron  on  heating,  or  by 
mixing  moist  hydrated  oxide  of  iron  with  asbestos  fiber  and  iron  filings. 

The  Dellwik-Fleischer  Wassergas-Ges.  m.  b.  H.*  prepare  iron  by 
the  reduction  of  a  mineral  oxide  which  retains  both  porosity  and  re- 
sistance after  repeated  use.  In  order  to  prevent  deposition  of  carbon 
during  the  reduction  of  the  iron  oxide  in  the  retort,  the  reducing  gas 
is  mixed  with  a  volume  of  steam  equal  to  at  least  half  the  sum  of  the 
carbon  monoxide  and  hydrocarbons  present  in  it.  It  is  also  found 
economical  to  carry  the  reduction  only  half  way  instead  of  completely 
to  the  metal,  and  this,  moreover,  gives  purer  hydrogen  since  no  carbon 
can  be  deposited  during  such  partial  reduction.  In  British  Patent 
7849,  of  1909,  the  Dellwik-Fleischer  Co.  make  use  of  iron  pyrites 
roasted  to  expel  all  sulfur  and  volatile  metals. f 

Hydrogen  gas  is  produced  according  to  Hills  and  Lane  J  by  passing 
steam,  preferably  superheated,  over  iron  contained  in  heated  retorts; 
and  the  mixture  of  hydrogen  and  steam  is  led  through  coolers,  from 
which  the  hydrogen  passes  to  a  gasometer.  By  means  of  reversing 
valves,  controlling  inlet  and  outlet  passages,  a  reducing  gas,  such  as 
water  gas,  coal  gas  or  the  like,  is  then  led  through  the  retorts  to  reduce 
the  iron  oxide  formed,  and  then  steam  is  again  passed. through.  Lane 
and  Monteux  §  secure  the  production  of  pure  or  nearly  pure  hydrogen 
in  a  continuous  manner  by  the  action  of  steam  on  red-hot  iron.  Finely- 
divided  iron  is  contained  in  a  series  of  vertical  retorts,  heated  exter- 
nally by  gas,  in  combination  with  a  regenerative  system.  The  retorts 
are  so  connected  that  a  current  of  steam  passes  through  some,  while 
the  iron  oxide,  already  formed,  is  being  reduced  in  others  by  a  stream 
of  reducing  gas  sent  in  the  opposite  direction.  Oxidation  and  reduc- 
tion thus  take  place  alternately,  oxidation  being  found  to  occupy  only 
half  the  time  of  reduction.  The  hydrogen  produced  is  cooled  and 
purified,  to  remove  traces  of  carbon  dioxide,  etc.  The  reducing  gas 
is  made  in  a  producer,  and  by  introducing  an  excess  of  steam,  it  be- 
comes rich  in  hydrogen.  The  excess  of  reducing  gas  is  utilized  for 
heating  the  retorts.  After  repeated  use  the  iron  becomes  inactive, 
owing  to  an  accumulation  of  impurities,  but  if  these  are  burned  away 

*  French  Patent  395,132,  Oct.  10,  1908. 

t  British  Patent  21,479,  Oct.  10,  1908,  and  7849,  April  1,  1909. 

J  British  Patent  10,356,  May  7,  1903. 

§  French  Patent  386,991,  Feb.  7,  1908. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      487 

by  the  occasional  admission  of  air,  the  efficiency  of  the  iron  is  said  to 
be  restored. 

As  it  has  been  found  in  practice  that  the  reducing  reaction  takes  considerably 
longer  than  the  generation  of  hydrogen,  the  Lane  process  (British  Patent  17,591, 
July  29,  1909)  may  be  carried  out  in  three  or  more  groups  of  retorts,  the  greater  part 
of  which  are  constantly  subjected  to  the  action  of  reducing  gases  for  the  regeneration 
of  the  iron,  or  other  hydrogen-producing  substance.  The  retorts  communicate 
with  one  another  by  means  of  a  series  of  pipes,  fitted  with  controlling  valves,  so 
that  steam  or  the  reducing  gases  may  be  admitted  as  required.  The  hydrogen, 
which  is  evolved  in  the  first  few  minutes  of  the  operation,  being  impure,  is  diverted 
from  the  collector  of  pure  hydrogen,  and  mixed  with  the  water  gas  used  for  reduction. 
A  considerable  excess  of  water  gas  is  used  for  reduction,  and  it  undergoes  a  very 
thorough  system  of  purification  before  being  admitted  to  the  retorts;  the  excess, 
which  issues,  is  freed  from  the  accompanying  steam  and  used  again.  Means  are 
provided  for  forcing  hot  air  through  the  reaction  chamber,  which  is  done  periodically 
between  the  two  reactions  so  as  to  burn  out  objectionable  impurities,  especially 
sulfur.  For  the  purification  of  the  excess  of  water  gas,  or  other  reducing  medium, 
which  issues  unchanged  from  the  reducing  retorts,  the  gas  is  passed  into  a  cooler 
and  washer,  which  removes  mechanical  impurities,  and  thence  into  a  compressor. 
From  the  latter  it  passes  under  a  pressure  of  several  atmospheres  into  a  strong 
receiver.  The  latter  contains  coke  or  the  like  material,  down  which  cold  water  is 
distributed  by  means  of  a  pump  or  other  forcing  device.  The  compressed  gas, 
coming  into  contact  with  cold  water,  is  freed  from  such  impurities  as  sulfur  dioxide, 
hydrogen  sulfide,  carbon  dioxide,  etc.,  either  by  solution  or  by  condensation,  being 
at  the  same  time  deprived  of  the  greater  part  of  its  moisture.* 

With  the  Lane  and  similar  apparatus  it  has  been  found  f  that  the 
hydrogen  gas  obtained  contains  a  relatively  large  proportion  of  gaseous 
and  solid  bodies  or  impurities,  produced  concurrently  with  the  hydro- 
gen and  whose  presence  considerably  increases  the  quantity  of  reducing 
gas  necessary  for  carrying  out  the  reduction  operation,  as  well  as  the 
time  necessary  for  effecting  the  deoxidation  of  the  contact  material. 
The  presence  of  these  impurities  in  the  hydrogen  gas  is  due  to  the  fact 
that  the  reducing  agent  contains  sulfur,  carbon,  etc.,  which  either 
become  deposited  on  the  contact  material  or  generate  gases  such  as 
sulfurous  acid,  sulfuretted  hydrogen  or  carbon  dioxide.  After  the 
reduction  phase  a  certain  quantity  of  free  reducing  gas  still  remains 
in  the  retort,  the  presence  of  which  contaminates  the  hydrogen  and 
consequently  lessens  its  commercial  value. 

Lane,  therefore,  proposes  means  for  removing  the  reducing  gas  as 
well  as  the  sulfur,  carbon  and  other  impurities  between  the  two 
oxidizing  and  reducing  steps  of  the  process.  To  this  end  the  retort 
is  provided  at  each  extremity  with  a  multiple-way  controlling  valve 
adapted  to  establish  communication  between  that  end  of  the  retort 

*  Lane,  British  Patent  11,878,  Jan.  29,  1910. 
t  Lane,  U.  S.  Patent  1,028,366,  June  4,  1912.J 


488 


THE  HYDROGENATION  OF  OILS 


and  any  one  of  three  pipes  connected  respectively  at  the  one  end  of  the 
retort  to  a  supply  of  air  under  pressure,  a  supply  of  reducing  gas,  and 
a  hydrogen  receiver,  and  at  the  opposite  end  of  the  retort  respectively 
to  an  outlet,  a  gas-washing  and  regenerating  apparatus,  and  a  supply 
of  steam  under  pressure. 

In  Fig.  72  A  is  the  retort  provided  with  an  inlet  B  at  the  lower  end  and  an  outlet 
C  at  the  upper  end,  and  F  and  G  are  four-way  valves  which  are  capable  of  being 
rotated  by  means  of  hand-wheels  H  and  J  so  as  to  open  communication  on  the  one 
hand  between  the  retort  A  and  either  the  pipe  K  connected 
to  a  hydrogen  container,  a  pipe  M  connected  to  a  supply 
of  reducing  gas,  or  a  pipe  N  connected  to  a  supply  of  air 
under  pressure,  and  on  the  other  hand  either  with  a  dis- 
charge pipe  0,  a  pipe  P  leading  to  a  gas-washing  or  regen- 
erating apparatus  and  a  pipe  Q  connected  to  a  supply  of 
low-pressure  steam.  Assuming  that  the  contact  material 
in  the  retort  has  been  oxidized  during  the  previous  hydro- 
gen-producing phase,  the  sequence  of  operations  is  as 
follows.  In  the  first  place  the  impurities  deposited  on  the 
contact  material  during  the  previous  reduction  phase,  or 
present  in  the  gaseous  state  in  the  retort,  are  removed  by 
effecting  their  combustion.  This  is  effected  by  rotating 
the  valve  G  one-quarter  of  a  revolution  so  as  to  admit 
air  under  pressure  to  the  lower  part  of  the  retort  through 
the  pipes  N  and  D,  and  rotating  valve  F  so  as  to  force 
out  the  products  of  combustion  into  the  atmosphere 
through  the  pipes  E  and  0.  The  valve  G  is  then  rotated 
so  as  to  admit  reducing  gas  to  the  retort  through  pipes 
M  and  D  and  rotating  valve  F  so  as  to  open  communi- 
cation between  the  upper  part  of  the  retort  and  the  gas- 
washing  or  regenerating  apparatus  through  pipes  E  and  P. 
At  the  completion  of  the  reducing  phase  the  valve  F  is 
rotated  so  as  to  connect  the  upper  part  of  the  retort  with 
the  supply  of  steam  under  pressure  through  pipes  Q  and 
E,  whereupon  the  pressure  of  the  steam  being  greater 
than  that  of  the  reducing  gas  remaining  in  the  retort,  the  latter  is  forced  out 
through  pipes  D  and  M  carrying  with  it  the  impure  hydrogen  which  has  been 
generated  by  the  action  of  the  steam  on  the  sulfur,  carbon,  etc.,  deposited  on  the 
contact  material.  As  soon  as  it  is  found  that  the  hydrogen  passing  out  through 
pipe  M  is  sufficiently  pure  the  valve  G  is  rotated  so  as  to  deliver  the  gas  to  the 
hydrogen  container,  after  which,  air  is  then  again  passed  through  the  retort  in  the 
manner  previously  described.* 

*  Lane  (U.  S.  Patent  1,040,218,  Oct,  1,  1912)  purifies  the  reducing  gas  in  the 
manufacture  of  hydrogen  by  the  alternate  oxidation  and  deoxidation  of  iron,  by 
compressing  the  reducing  gas  to  a  pressure  of  several  atmospheres  and  then  causing 
it  to  flow  (while  still  under  pressure)  in  contact  with  an  oppositely  flowing  stream 
of  water.  To  increase  the  effectiveness  of  the  washing  operation,  the  gas  is  passed 
through  a  coke  tower  through  which  water  is  flowing  in  an  opposite  direction. 


FIG.  72. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      489 

Fig.  73  shows  the  Lane  system  as  installed  in  the  works  of  a  large 
soap  manufacturer  in  England.  Figs.  74  and  75  show  the  same  system 
installed  at  a  plant  near  Paris. 

Lane  states  *  that  in  practice  it  has  been  found  difficult  to  obtain 
pure  hydrogen  in  consequence  of  the  steam  admitted  to  the  retort 
during  the  oxidation  state  coming  into  contact  with  the  reducing  gas 
admitted  during  the  previous  reduction  state  and  with  the  sulfur, 
carbon,  etc.,  associated  with  and  introduced  into  the  retort  by  this 


FIG.  73. 

gas,  the  result  of  which  contact  being  the  formation  of  sulfuretted 
hydrogen,  sulfurous  acid,  carbon  dioxide,  etc.,  and  consequent  con- 
tamination of  hydrogen  produced  by  the  action  of  the  steam.  Lane 
proposes  to  remove  the  sulfur,  carbon  and  other  impurities  left  by  the 
reduction  phase,  by  admitting  air  under  pressure  to  the  retort  and 
discharging  the  products  of  combustion  into  the  atmosphere.  The 
admission  of  air  to  the  retort  and  the  discharge  of  the  products  of 
combustion  then  ceases  and  reducing  gas  is  admitted  and  passed 
through  and  out  of  the  retort  to  a  gas-washing  and  regenerating  appara- 
tus. When  the  reduction  stage  has  been  completed  the  admission  of 
reducing  gas  is  shut  off  and  steam  admitted.  As  a  certain  proportion 
of  reducing  gas  will  then  be  present,  impure  hydrogen  will  be  produced 
and  this  is  allowed  to  go  to  waste,  until  the  product  is  found  to  be 
sufficiently  pure.  Thereupon  the  outlet  to  the  atmosphere  is  closed 
and  the  hydrogen  passed  into  a  storage  tank. 

*  U.  S.  Patent  1,078,686,  Nov.  18,  1913. 


490 


THE  HYDROGENATION  OF  OILS 


A  process  devised  by  Messerschmitt  *  depends  upon  the  alternate 
oxidation  of  spongy  iron  by  means  of  steam,  with  the  evolution  of 


FIG.  74. 

hydrogen,  and  the  reduction  of  the  resulting  iron  oxide  f  by  means  of 
reducing  gases,  such  as  water  gas. 


FIG.  75. 

*  French  Patent  444,105,  May  22,  1912. 

f  After  iron  oxide  has  been  used  for  a  time  it  becomes  partially  or  wholly  inac- 
tive and  has  to  be  replaced  by  fresh  material.  It  has  been  proposed  to  make  the 
reducing  chamber  vertical  with  a  grate  at  the  bottom  through  which  the  spent  oxide 
may  be  removed  from  time  to  time  just  as  ashes  are  withdrawn  from  a  gas  producer. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      401 

An  upright,  cylindrical  reaction  chamber  made  of  iron  is  suspended  inside  a 
furnace  chamber,  with  which  it  is  in  open  communication  at  the  bottom,  the  lower 
end  of  the  cylinder  being  provided  with  a  grate  to  support  the  column  of  reacting 
material.  The  width  of  the  reaction  cylinder  is  relatively  small,  so  that  the  contents 
may  readily  be  heated  from  all  sides,  and  the  furnace  chamber  is  provided  with 
checkerwork  constituting  a  superheater.  Both  the  reaction  cylinder  and  the 
furnace  chamber  are  capable  of  being  sealed,  and  are  provided  with  a  system  of 
pipes  and  valves,  enabling  the  introduction  of  either  steam  or  water  gas  into  the 
reaction  cylinder  or  the  furnace  chamber.  An  air-supply  pipe  communicates  with 
the  furnace  chamber,  and  a  pipe  leading  from  the  top  of  the  reaction  cylinder  can 
be  put  into  communication  with  a  gas  purifier  and  the  steam-raising  plant.  The 
process  is  carried  out  in  three  phases ;  water  gas  and  air  are  first  burned  in  the  furnace 
chamber  until  the  material  inside  the  reaction  cylinder  has  reached  the  required 
temperature.  The  air  supply  is  then  cut  off  and  water  gas,  flowing  in  at  the  bottom 
of  the  furnace,  becomes  strongly  heated,  enters  the  open  lower  end  of  the  cylinder, 
traverses  the  mass  of  iron  oxide  in  an  upward  direction,  and  finally  passes  off  at 
the  top  to  the  steam-raising  plant,  where  any  combustible  gases  are  utilized.  When 
the  reduction  of  the  iron  oxide  is  complete  the  supply  of  water  gas  is  cut  off  and 
steam  is  introduced,  first  into  the  bottom  of  the  furnace  to  sweep  out  any  residual 
gases  from  the  second  operation  (the  furnace  being  in  direct  communication  with 
the  chimney  while  this  is  going  on),  and  then  into  the  top  of  the  furnace  chamber, 
from  which  it  passes  downwards  through  the  hot  checker-work  and  finally  upwards 
through  the  mass  of  spongy  iron.  Hydrogen  issues  from  the  top  of  the  reaction 
cylinder  and  travels  through  a  purifier  into  a  gasometer.  The  iron  receptacle  may 
take  the  form  of  two  concentric  cylinders,  the  reaction  material  being  in  that  case 
charged  into  the  annular  space  between  the  two.  The  cylinders  are  periodically 
heated  and  reduced  by  means  of  the  reducing  gases,  both  inside  and  outside. 

Messerschmitt  has  proposed  to  use  compact  iron  (wrought  iron  or 
steel)  as  a  support  for  spongy  iron ;  only  the  surface  layers  of  the  com- 
pact iron  taking  part  in  the  reaction.  The  spongy  iron,  may,  for 
example,  be  placed  in  the  channels  of  a  number  of  iron  bars  of  U-shaped 
cross-section,  or  in  perforated  moulds,  tubes,  boxes  or  troughs  of 
compact  iron.* 

Elworthy  f  asserts  that  the  various  apparatus  proposed  for  the  pro- 
duction of  hydrogen  by  the  steam  and  iron  method  are  subjected  to 
serious  drawbacks  in  practice,  owing  to  the  liability  of  the  iron  to  cake 
together  and  to  its  difficulty  of  access  and  removal. 

The  iron  rapidly  cakes  and  chokes,  so  that  the  steam  or  gas  comes  into 
contact  with  only  a  small  proportion  of  the  active  surface  and  loss  of  efficiency 
results.  It  is  thus  frequently  necessary  to  remove  and  replenish  the  iron;  but  this 
is  a  troublesome  operation,  owing  to  the  construction  of  the  furnace  and  difficulty 
of  the  removal  of  the  iron.  Hence  Elworthy  places  the  iron  in  finely-divided  form 
in  a  large  number  of  separate  trays  of  refractory  fire-brick  or  the  like,  each  adapted 
to  contain  a  shallow  layer  of  iron  in  finely-divided  form  and  to  be  built  up  in  succes- 
sive layers  from  bottom  to  top  of  the  furnace,  so  as  to  form  a  close-lying  refractory 

*  British  Patent  12,117,  May  22,  1912. 
t  U.  S.  Patent  778,182,  Dec.  20,  1904. 


492 


THE  HYDROGENATION  OF  OILS 


filling  (Fig.  76).  The  trays  are  open  at  their  ends  to  enable  the  steam  or  gas  to 
pass  freely  over  them  in  contact  with  the  iron  when  built  up,  and  they  have  sup- 
porting flanges  for  supporting  the  under  face  of  one  tray  at  a  suitable  distance  from 
the  material  on  the  tray  below,  and  this  under  face  of  the  tray  radiates  a  quantity 
of  heat  onto  the  shallow  layer  of  metallic  iron  during  the  heat-absorbing  or  oxidizing 

stage,  while  at  the  same  time  super- 
heating the  steam  as  it  passes  along 
the  narrow  shallow  channel  between 
the  upper  and  lower  series  of  trays. 
When  the  trays  are  built  up  in  the 
furnace,  they  form  a  number  of  nar- 
row flues  containing  a  shallow  layer 
of  iron  and  running  in  a  zigzag  course 
from  bottom  to  top  of  the  furnace 
and  affording  free  passage  for  the 
steam  or  reducing  gas.  These  narrow 
flues,  so  to  speak,  divide  up  the  mass 
of  refractory  material  into  a  cellular 
structure  such  that  the  gases  can 
pass  freely  through  the  cell  flues  over 
the  iron. 

Messerschmitt  *  employs  spongy 
iron  produced  from  fragmentary  oxide 
iron  ore  (i.e.,  an  ore  containing 
Fc2Os).  Only  spongy  iron  produced 
from  such  oxidized  iron  ore  is  re- 
garded by  Messerschmitt  as  pos- 
sessing the  requisite  porosity  and 
strength  for  carrying  out  the  proc- 
ess. 

The  effect  of  using  ferric  oxide  as  raw  material,  it  is  claimed,  is  that  the  oxide 
after  reduction  becomes  porous  throughout  its  entire  mass  on  account  of  the  de- 
crease in  volume  consequent  upon  the  removal  of  the  oxygen  therefrom  and  thus 
an  increased  surface  is  exposed  to  the  subsequent  action  of  the  steam.  The  use  of 
ferric  oxide  in  the  form  of  oxide  ores  is  important  because  the  lumps  of  this  ore,  in 
consequence  of  its  peculiar  natural  texture,  maintain  their  shape  in  spite  of  repeated 
reductions  and  oxidations  and  the  ore  possesses  the  necessary  strength  to  withstand 
the  pressure  of  superimposed  layers;  if  this  were  otherwise  the  path  for  the  gases 
would  become  choked  by  the  crumbling  of  the  ferric  oxide  and  continuous  working 
would  be  impeded.  The  gangue,  clay,  silica  and  other  components  of  the  ore  have 
for  effect  to  prevent  (in  spite  of  high  temperatures  which  may  be  produced  either 
intentionally  or  in  consequence  of  irregular  working  of  the  furnace)  a  sintering  of 
the  charge,  the  latter  thus  constituting  a  sort  of  rigid  incombustible  carrier  for  the 
oxides  and  the  iron  sponge. 

The  presence  of  carbon  monoxide  in  hydrogen  gas-mixtures  as  at  present  produced 
by  the  action  of  steam  on  reduced  iron  is  to  be  ascribed  to  the  following:  If  ferric 
oxide  be  reduced  by  means  of  carbon  monoxide  metallic  iron  and  carbon  dioxide 
are  formed,  but  simultaneously  a  considerable  quantity  of  carbon  is  precipitated 
from  the  carbon  monoxide.  Hence,  if  after  completion  of  the  reduction  phase  of 

*  U.  S.  Patent  971,206  of  Sept.  27,  1910. 


FIG. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      493 

the  process,  steam  be  led  over  the  mixture  containing  spongy  iron  thereby  produced, 
there  is  produced  not  only  hydrogen  according  to  the  equation, 

3  Fe  +  4  H2O  =  Fe304  +  4  H2, 

but  also  at  the  same  time  carbon  monoxide  and  carbon  dioxide  resulting  from  the 
reaction  of  the  steam  on  the  carbon  present,  thus  contaminating  the  hydrogen. 
Since  the  carbon  present  is  incompletely  decomposed  by  the  steam  at  the  compara- 
tively low  temperatures  used,  the  carbon  increases  more  and  more  by  the  repeti- 
tion of  the  cycles  (i.e.,  of  the  reduction  and  oxidation  phases  of  the  process)  and 
consequently  the  impurity  of  the  resulting  hydrogen  becomes  greater  and  greater. 
From  this  the  necessity  of  employing  means  for  the  prevention  of  the  precipitation 
of  carbon  during  the  reduction  phase  will  be  evident.  The  precipitation  of  carbon 
from  the  heated  carbon  monoxide  takes  place,  according  to  the  equation, 

2CO  =  C  +  C02. 

In  order  to  prevent  this  precipitation  of  carbon  the  following  method  is  used  by 
Messerschmitt: 

The  gases  destined  for  reduction  and  containing  carbon  monoxide  and  hydro- 
carbons are  mixed  with  a  quantity  of  steam  such  that  the  steam  volume  amounts, 
at  the  most,  to  half  of  the  volume  of  the  carbon  monoxide  plus  that  of  the  hydro- 
carbons. For  reducing  the  ferric  oxide  (or  Fe3O4)  this  mixture  may  be  directly  led 
into  the  retorts  or  tubes  containing  the  iron  oxide  without  a  considerable  amount  of 
carbon  being  precipitated.  The  reason  of  this  result  is  explained  as  follows:  If 
carbon  monoxide  be  mixed  with  steam,  hydrogen  and  carbon  dioxide  are  formed 
and  the  volume  of  the  first  is  the  same  as  that  of  the  carbon  monoxide  transformed 
into  dioxide  by  the  oxidation.  In  place  of  CO  therefore  an  equal  volume  of  H2  and 
an  equal  volume  of  CO2  is  formed  according  to  the  equation, 

CO  +  H2O  =  H2  +  CO2. 

In  general  the  reaction  with  hydrocarbons  is  as  follows: 

CmHn  +  2  mH2O  =  2  mH2  +  nH  +  mCO2. 

For  every  volume  of  hydrocarbon  therefore  one  volume  of  CO2  and  more  than 
two  volumes  of  hydrogen  are  formed.  Now  as  only  half  of  the  carbon  monoxide 
is  oxidized  by  the  steam  to  CO2  (since  the  amount  of  steam  added  is  only  half  that 
of  the  CO)  as  final  product  a  gas  of  the  following  composition  is  obtained  according 
to  the  equation, 

2  CO  +  H2O  =  CO  +  H2  +  CO2. 

The  gas  used  for  reduction  of  the  iron  therefore  would  yield  for  every  volume  of 
carbon  monoxide  one  volume  of  hydrogen  and  one  volume  of  carbon  dioxide,  or 
for  two  volumes  of  reducing  gases  one  volume  of  carbon  dioxide.  This  proportion, 
however,  should  not  be  changed  on  account  of  the  reducing  gases  because  otherwise 
the  reduction  of  the  Fe3O4  to  metal  no  longer  takes  place.  For  this  reason  the 
addition  of  steam  is  restricted  according  to  the  above  equation  in  order  that  the  gas 
and  steam  mixture  may  be  used  directly  for  the  reduction  of  the  iron.  This  reduc- 
ing gas  of  the  composition  CO  +  H2  -f  CO2,  however,  precipitates  considerably  less 
carbon  during  the  reduction  than  pure  carbon  monoxide  or  carbon  dioxide  mixed 
with  nitrogen  (producer  gas)  would  do.  The  reason  for  this  lies  in  the  presence  of 
the  hydrogen.  The  latter  first  attacks  the  ferric  oxide  with  the  formation  of  steam 


494  THE  HYDROGENATION  OF  OILS 

which  again  reacts  on  the  carbon  monoxide  and  thus  again  produces  hydrogen 
and  carbon  dioxide.  By  this  means  the  carbon  monoxide  tending  to  precipitate 
carbon  is  continually  reduced,  whereas  the  carbon  dioxide  and  the  hydrogen  (neither 
of  which  precipitates  carbon)  is  increased.  From  this  Messerschmitt  concludes 
that  the  presence  of  hydrogen  considerably  restricts  the  precipitation  of  carbon  from 
the  carbon  monoxide.  Hence  Messerschmitt  proposes  to  provide  for  the  addition  of 
steam  in  such  manner  that  its  volume  only  amounts  to  about  half  of  the  combined 
volume  of  the  carbon  monoxide  and  that  of  the  hydrocarbons  contained  in  the  gas. 
The  reduction  of  ferric  oxides  to  spongy  iron  by  means  of  reducing  gases  takes 
place  very  gradually,  the  iron  being  gradually  reduced  to  lower  stages  of  oxidation 
according  to  the  following  equations, 

3  Fe2O3  +  CO  =  2  Fe3O4  +  CO2, 

2  Fe3O4  +  CO  =     Fe«O7  +  CO2, 

Fe3O4  +  CO  =  3  FeO     +  CO2, 

from  which  combinations  metallic  iron  is  formed  by  a  further  reduction  according 
to  the  equation, 

+  7  CO  =  3  Fe2  -+~7  CO2. 


A  surplus  of  reducing  gas  is  necessary  in  order  to  render  the  reduction  to  spongy 
iron  complete.  Since  between  the  products  of  oxidation  (CO2,  H2O)  produced  and 
the  reducing  gases  (CO,  H,  CnHm)  a  relationship  of  equal  weights,  according  to 
Messerschmitt,  subsists  which  is  not  affected  even  by  prolonged  reaction  on  the 
ore,  the  waste  gas  of  the  reduction  always  contains  a  considerable  amount  of  reduc- 
ing gases.  The  more  unfavorable  the  proportion  of  undecomposed  and  decomposed 
gases  in  the  waste  gases  becomes,  the  more  difficult  it  is  to  reduce  the  ore.  Reduc- 
tion takes  place  easily  at  the  beginning,  whereas  it  becomes  more  difficult  as  the  ore 
becomes  poorer  in  oxygen  and  the  further  reduction  to  spongy  iron  has  progressed. 
It  is  immaterial  for  the  production  of  the  hydrogen  whether,  during  the  reduction 
phase  metallic  iron  or  a  lower  stage  of  oxidation  than  that  of  black  oxide  of  iron  is 
produced,  since  Fe  as  well  as  FeO  and  FeeOy  for  instance  are  oxidized  to  Fe3O4  when 
acted  on  at  incandescence  by  means  of  steam  while  giving  off  hydrogen  according 
to  the  formula, 

3  Fe  +  4  H20  =  Fe304    +  4  H2, 

Fe6O7  +  H2O     =2  Fe3O4  +  H2. 

Now  it  has  been  found  that  the  proportion  of  the  gases  necessary  for  the  reduction 
relatively  to  the  hydrogen  produced  during  the  oxidation  phase  remains  relatively 
small  and  that  efficient  working  is  secured  if  the  reduction  of  the  ferric  oxide 
(Fe3O4)  during  the  reduction  phases  is  only  incompletely  effected  (at  most  only  half 
reduced)  . 

By  the  reaction  of  the  steam  during  the  oxidation  phase,  several  gases,  methane, 
carbon  dioxide  and  hydrocarbons,  are  formed  from  carbon  iron  combinations,  con- 
taminating the  hydrogen.  Absorption  of  carbon  is  impossible  as  long  as  (in  addition 
to  spongy  iron)  a  surplus  of  oxides  is  contained  in  the  ore.  If,  for  instance,  carbon 
were  actually  taken  up  it  would  of  necessity  have  to  be  decomposed  again  by  the 
oxygen  of  the  oxide  present,  according  to  the  equation, 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      405 


A  simple  form  of  apparatus  devised  by  Messerschmitt  *  is  shown 
in  Fig.  77.  The  contact  material  in  this  case  is  iron  in  the  form  of 
tubes.  These  are  shown  at  d  in  the  furnace  chamber  /.  The  tubes  d 
slip  over  the  upright  tubes  c  projecting  from  the  top  of  the  distrib- 
uting chamber  b.  A  filling  of  sand  around  the  base  of  these  tubes  d 
seals  them  and  yet  allows  their 
ready  removal  when  replacement 
is  required.  The  reducing  gas  is 
introduced  by  the  inlet  a.f 

In  another  type  of  furnace  for 
the  production  of  hydrogen  from 
reduced  iron  and  steam,  Messer- 
schmitt t  makes  use  of  apparatus 
as  shown  in  Fig.  78.  The  reaction 
is  carried  out  at  different  planes  in 
this  furnace.  The  walls  are  pro- 
vided at  different  heights  with 
heating  channels  cc.  The  gas  and 
air  nozzles  1,  2,  3  and  4  are  so  dis- 
posed that  the  heating  gases  are  discharged  tangentially  into  the 
furnace  in  such  a  manner  as  to  prevent  local  overheating  of  the  iron. 
The  oxidized  iron  in  the  different  zones  of  the  furnace  is  successively 
reduced  and  heated  and  the  waste  gases  from  one  zone  are  burned 
by  the  aid  of  a  blast  of  air  in  a  higher  zone.  In  the  upper  part  of 
the  structure  the  checkerwork  g  enables  preheating  of  the  reducing 
gas  and  steam. 

Natural  ores  of  manganese  or  of  manganese  and  iron  are  employed 
by  Messerschmitt  §  in  place  of  ordinary  iron  ore.  It  is  stated  that 
hydrogen  is  obtained  in  good  yields  at  700°  to  800°  C.  or  about  200 
degrees  lower  than  with  iron  sponge. 

*  Chem:  Ztg.  Rep.  (1913),  521. 

t  A  description  of  apparatus  recently  recommended  by  Messerschmitt  appears 
in  Chem.  Zeit.  Rep.  (1913),  696.  (German  Patents  266,863,  July  9,  1911,  and 
267,594,  Feb.  9,  1912.)  Messerschmitt  has  also  taken  out  German  Patent  268,339, 
Oct.  18,  1912,  supplementing  patent  No.  267,594.  (Chem.  Zeit.  Rep.  (1914),  31.) 
A  method  for  the  manufacture  of  hydrogen  by  the  alternate  oxidation  and  reduc- 
tion of  iron  is  described  by  Messerschmitt  in  German  Patent  268,062,  Nov.  3,  1912. 
(Chem.  Zeit.  Rep.  (1914),  22,  and  Zeitsch.  f.  angew.  Chem.  (1914),  47,  No.  5;  (1914), 
61,  No.  7.)  See  also  German  Patent  263,390,  July  24,  1912. 

I  Chem.  Zeit.  Rep.  (1913),  521;  German  Patent  263,391,  July  26,  1912. 

§  J.  S.  C.  I.,  1914,  201;  French  Patent  461,480,  Aug.  19, 1913.  Additional  methods 
employed  by  Messerschmitt  for  the  generation  of  hydrogen  are  described  in  J.  S.  C.  I., 
1914,  313. 


496 


THE  HYDROGENATION  OF  OILS 


An  apparatus  employed  by  the  Internationale  Wasserstoff-Aktien- 
Gesellschaft  is  shown  in  Fig.  79.  On  the  left  is  a  gas  producer  sup- 
plying fuel  gas  to  heat  the  two  vertical  retorts  shown  on  the  right. 
The  heating  gases  and  products  of  combustion  move  in  the  direction 
indicated  by  the  arrows  and  finally  pass  to  an  exit  flue.  The  valves 


FIG.  78. 


a  and  b  are  opened  and  water  gas  flows  through  the  iron  ore  filling  the 
retorts,  reducing  iron  oxide  to  finely-divided  metallic  iron.  When 
reduction  has  sufficiently  progressed  the  valves  a  and  6  are  closed  and 
the  three-way  valve  c  is  opened.  Steam  is  admitted  by  the  valve  d 
and  hydrogen  is  withdrawn  at  e.  When  the  iron  becomes  reoxidized 
the  steam  is  shut  off  and  the  oxide  again  reduced  by  water  gas.  The 
reducing  gases  after  passage  through  the  retorts  are  burned  in  the 
combustion  chamber.  The  hydrogen  exhibits  a  purity  approaching 
98  per  cent  at  a  cost  of  4  cents  per  cubic  meter.* 

The  above  concern  f  employs  iron  pyrites  waste  as  raw  material, 

*  Chemie  der  Case,  Brahmer,  Frankfort  (1911),  93. 

t  It  should  be  stated  that  the  Internationale  Wasserstoff-Aktiengesellschaft  of 
Germany  is  the  owner  of  a  considerable  number  of  processes  and  patents  (Iwag 
System)  on  the  production  of  hydrogen. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      497 


FIG.  79. 


w 


t 

© 

E 


FIG.  80. 


498  THE  HYDROGENATION  OF  OILS 

which  has  been  deprived  of  sulfur,  arsenic  and  zinc  by  roasting; 
this  material  is  porous  and  refractory  and  retains  these  properties 
after  repeated  use.* 

By  another  process  a  ferruginous  mass  is  treated  alternately  with 
steam  and  a  purified  reducing  gas,  both  of  which  are  preheated  in 
regenerators  situated  outside  the  reaction  furnace,  so  as  practically 
to  avoid  transference  of  heat  by  conduction  from  these  to  the  furnace. 
The  reducing  gas  leaving  the  reaction  furnace  is  burned  with  oxygen 
or  air  in  the  regenerators,  and  the  process  may  be  made  continuous 
by  employing  two  or  more  regenerators  with  a  central  furnace,  and 
passing  steam  and  gas  through  the  system,  first  in  one  and  then  in  the 
opposite  direction.! 

In  Fig.  80  is  shown  a  hydrogen-generating  apparatus  designed  by 
Strache.J  K  is  a  gas  producer,  the  gas  from  which  passes  through 
the  reaction  chamber  E,  containing  iron  filings,  and  is  burned  in  the 
checkerwork  R.  On  passing  steam  through  the  checkerwork  in  a 
reverse  direction  the  steam  becomes  superheated  and  when  brought 
into  contact  with  the  iron  filings  in  E  hydrogen  is  produced  and  is 
withdrawn  at  W.  Another  apparatus  designed  by  Strache  §  is  shown 
in  Fig.  81.  The  water-gas  generator  2,.  provided  with  inlets  25  and  4, 
for  steam  and  air  respectively  is  connected  with  the  reaction  chamber 
6,  by  the  pipe  5,  provided  with  a  gas-discharge  pipe  24.  Just  above 
the  place  where  the  pipe  5  enters  the  reaction  chamber  is  a  baffle  22, 
and  on  the  opposite  side  of  the  chamber  is  a  similar  baffle  23.  A 
branch  from  the  air-supply  pipe  opens  just  below  the  baffle  22,  and 
similar  branches  open  at  8  and  9.  The  reaction  chamber  6  is  divided 
into  compartments  by  gratings  on  which  the  iron  reaction  material  is 
placed.  In  the  upper  part  of  the  chamber,  above  a  regenerator  10, 
are  purifying  retorts  11,  the  gas  to  be  purified  entering  by  20  and  the 
purified  product  leaving  by  21.  When  the  apparatus  has  been  brought 
to  the  proper  temperature  and  is  ready  for  the  production  of  hydrogen, 
steam  is  introduced  through  the  pipe  14,  below  the  valve  13,  so  as 
to  displace  any  gases  from  the  pipe  5  and  the  ash-pit  15.  Steam  is 
then  introduced  through  the  tube  18,  below  the  valve  12,  displacing 
gas  from  the  reaction  chamber  from  the  top  downwards.  The  hydro- 
gen produced  passes  away  through  19  to  a  holder,  from  which  it  may 
be  passed  through  the  pipe  20  into  the  purifying  retorts  11,  charged 
with  potash  lime. 

*  French  Patent  405,200,  July  19,  1909. 

t  British  Patent  2096,  Jan.  25,  1913,  Badische  Anilin  und  Soda  Fabrik. 

f  Brahmer,  Chemie  der  Gase,  91. 

§  German  Patent  253,705,  Oct.  26,  1910. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      4<)<> 

The  claim  is  made  by  Dieffenbach  and  Moldenhauer  *  for  the  use 
of  the  residue  left  on  roasting  spathic  iron  ore  in  the  air,  in  the  prep- 
aration of  iron  to  be  employed  in  the  decomposition  of  steam.  This 
material  is  very  porous,  and  is  in  most  cases  free  from  substances 
which  would  have  injurious  effects  in  the  manufacture  of  hydrogen. 
They  also  claim  f  the  use  of  alloys  of  iron  with  manganese,  chromium, 
tungsten,  titanium,  aluminium  or  other  similar  elements  as  the  primary 
materials.  These  have  the  advantage  that  they  are  not  fusible,  do 


FIG.  81. 

not  soften,  and  do  not  form  fusible  or  soft  compounds  with  iron  or  its 
oxides.  In  place  of  alloys,  mixtures  of  iron  or  its  oxides  with  the  other 
elements  specified,  or  their  oxides,  may  be  employed,  for  instance  in 
the  form  of  briquettes. 

In  the  preparation  of  hydrogen  by  the  alternate  action  of  steam  on 
iron  and  of  reducing  gases  on  ferric  oxide,  the  iron  soon  loses  its  activity 
owing  to  fritting,  etc.  The  Badische  Anilin  und  Soda  Fabrik  {  claim 

*  German  Patent  232,347,  Feb.  6,  1910. 

t  French  Patent  444,044,  May  20,  1912.  See  also  Zeitsch.  f.  angew.  Chem.,  1914, 
No.  25,  222. 

J  French  Patent  440,780,  Feb.  29,  1912. 


500  THE  HYDROGENATION  OF  OILS 

as  remedies:  the  use  of  fused  iron  oxides,  especially  in  conjunction 
with  refractory  and  difficultly  reducible  oxides  of  high  melting-point 
such  as  magnesia  or  zirconia,  the  iron  oxides  being  prepared  by  the 
fusion  of  metallic  iron  in  the  presence  of  air  or  an  oxidizing  agent; 
fused  iron  oxides  may  be  used  in  conjunction  with  a  silicate  as  well  as 
similar  naturally  occurring  minerals  such  as  magnetite.  The  Badische 
Anilin  und  Soda  Fabrik  *  also  recommend  spongy  iron  prepared  by 
the  reduction  of  minerals  or  oxides  of  iron  by  means  of  carbon,  employ- 
ing external  heating.  The  metal  is  said  to  retain  its  porosity  after 
repeated  use.  "  Spongy  Swedish  iron,"  prepared  in  the  above  manner, 
is  especially  suitable. 

The  Berlin- Anhaltische  Maschinenbau-A-G.f  has  an  apparatus  for 
making  hydrogen  by  the  iron-sponge  system  which  considerably  facili- 
tates the  handling  of  the  ore  and  the  regulation  of  the  temperature. 

Belou  t  prepares  hydrogen  by  causing  steam  (preferably  super- 
heated) to  pass  over  red-hot  iron  in  retorts.  Hydrogen  and  oxide  of 
iron  are  thus  formed.  The  hydrogen  passes  on  to  a  gas  holder  for  use, 
and  the  oxide  is  reduced  to  metallic  iron  again  by  the  introduction  of 
charcoal  dust.  This  latter  operation  generates  so  much  heat  that  the 
retort  is  again  immediately  ready  for  decomposing  steam.  By  using 
a  number  of  retorts  and  carrying  on  the  two  processes  of  decomposi- 
tion and  revivification  alternately,  the  production  of  hydrogen  may 
be  made  continuous.  Suitable  provision  is  made  for  the  removal  of 
the  carbon  monoxide  and  dioxide  formed  during  the  revivification. 

Highly-heated  tubes  of  refractory  earthenware,  partly  filled  with  iron  filings,  and 
in  which  a  partial  vacuum  has  been  previously  produced,  are  used  by  Oettli  (British 
Patent  16,759,  Sept.  4,  1885).  A  certain  proportion  of  hydrogen  is  added  to  the 
steam,  and  this,  together  with  the  action  of  the  iron  filings,  is  claimed  to  tend  to 
destroy  the  equilibrium  conditions  and  to  prevent  the  hydrogen  formed  by  the 
decomposition  of  the  steam  from  re-uniting  with  oxygen.  This  effect  is  said  to  be 
promoted  by  the  reduced  pressure  in  the  tubes,  and  by  the  loss  of  heat  due  to  the 
splitting  up  of  the  aqueous  vapor.  From  the  tubes  the  gases  pass  through  separators 
to  gas  holders. 

Vignon's  apparatus  §  consists  of  a  set  of  retorts  containing  iron 
oxide.  A  reducing  gas  is  led  from  a  gas  producer,  through  a  suitable 
purifier,  into  the  retorts  for  the  reduction  of  the  iron  oxide.  The  heat 
formed  thereby  is  utilized  for  the  regenerative  heating  of  the  air 
blast  for  the  producer.  The  heat  of  the  hydrogen  gas  produced  is  used 
for  superheating  the  steam.  A  set  of  four  valves  can  be  manipulated 

*  French  Patent  453,077,  Jan.  11,  1913. 

t  J.  S.  C.  L,  1914,  256,  and  British  Patent,  28,390,  Dec.  9,  1913. 

j  British  Patent  7518,  May  25,  1887. 

§  First  Addition,  dated  Dec.  27,  1907,  and  French  Patent  373,271,  Jan.  2,  1907. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS      501 

by  a  single  handle,  allowing  the  regulating  and  reversing  of  the  differ- 
ent gas  currents. 

The  process  of  Gerhartz  *  consists  in  blowing  steam  through  a 
molten  oxidizable  metal,  and  subsequently  reducing  the  oxidized  metal 
for  further  use.  Molten  iron,  for  example,  is  introduced  into  a  vessel 
lined  with  refractory  material  and  provided  with  a  perforated  false 
bottom  somewhat  after  the  manner  of  the  Bessemer  converter.  Steam 
under  pressure  is  blown  into  the  space  below  the  false  bottom  and  is 
decomposed  while  rising  through  the  molten  iron;  the  hydrogen  pro- 
duced is  led  off  through  a  suitable  pipe,  and  the  heat  carried  by  it  is 
utilized  for  generating  steam.  The  fluidity  of  the  molten  iron  is 
gradually  diminished,  and  after  a  time  the  supply  of  steam  is  stopped, 
coke  is  introduced  and  the  melt  is  blown  with  air  in  order  to  reduce 
the  iron  oxide  which  has  been  formed  and  thus  restore  the  fluidity  of 
the  molten  mass. 

A  process  brought  forward  by  The  Nitrogen  Co.f  involves  reacting 
with  steam  on  a  molten  or  heated  metal  having  a  strong  affinity  for 
oxygen,  which  is  thus  absorbed.  After  collecting  the  residual  hydro- 
gen, the  metallic  oxide  produced  is  made  to  dissolve  or  disseminate  in 
a  body  of  fused  salt  in  which  it  is  brought  into  contact  with  a  suitable 
reducing  agent,  the  reduced  metal  being  continuously  returned  for 
re-oxidation  in  the  process. 

Illuminating  gas,  water  gas  or  other  gas  containing  free  hydrogen, 
according  to  Jaubert,J  is  passed  through  retorts  packed  with  briquettes 
formed  of  iron  oxide  with  a  refractory  substance  and  a  catalytic  agent, 
the  retorts  being  heated  to  800°  to  900°  C.J  Steam  is  afterwards 
passed  through  the  retorts  at  the  same  temperature,  yielding  hydrogen. 
The  briquettes  are  preferably  composed  of  a  mixture  of  30  to  60  kilos 
of  iron  oxide  (Fe2O3  or  Fe3O4),  15  to  25  kilos  of  fire  clay  or  pumice,  15 
to  25  kilos  of  calcined  magnesia  and  5  to  15  kilos  of  the  oxide  of  lead 
copper,  chromium  or  manganese. 

The  decomposition  of  water  into  hydrogen  and  oxygen  by  the  action  of  con- 
centrated solar  rays  in  presence  of  finely-divided  iron  and  apparatus  for  effecting 
this  is  described  by  Claver.§ 

In  the  manufacture  of  hydrogen  by  alternately  passing  steam  over 
iron,  and  water  gas  over  the  iron  oxide  thus  formed,  Caro  ||  has  devised 
a  system  by  which  portions  of  the  water  gas  are  burned  in  different 

*  German  Patent  226,543,  June  23,  1909. 

t  British  Patent  17,666,  Aug.  3,  1911. 

j  Jaubert,  French  Patent  418,312,  Sept.  23,  1909. 

§  British  Patent  21,468,  Nov.  12,  1895. 

II  German  Patent  249,269,  Aug.  30,  1910. 


502  THE  HYDROGENATION  OF  OILS 

parts  of  the  reaction  chamber,  so  that  in  addition  to  the  reduction  of 
the  iron  oxide,  a  superheating  of  the  reduced  iron  is  effected.  It  is 
claimed  that  by  working  in  this  manner,  the  gas-making  period  can  be 
considerably  prolonged. 

Steam  and  hydrocarbons  (such  as  those  derived  from  iron  carbides) 
are  passed  over  red-hot  iron  which  has  been  mixed  with  (preferably 
5  to  10  per  cent  of)  copper,  lead,  vanadium  or  aluminium,  either  to- 
gether or  separately.  These  metals  according  to  Saubermann  *  cata- 
lytically  accelerate  the  reaction  between  steam  and  iron,  and  also 
decompose  the  hydrocarbons. 

The  action  of  mixtures  of  carbon  monoxide  and  hydrogen  on  iron 
oxides  is  discussed  by  Gautier  and  Clausmann.f  They  passed  a 
mixture  of  3  volumes  of  carbon  monoxide  and  1  volume  of  hydrogen 
at  500°  C.  over  the  ferroso-ferric  oxide  derived  from  the  calcination 
of  a  native  ferrous  carbonate.  The  substance  formed  contained  about 
7  per  cent  of  carbon,  and  93  per  cent  of  ferrous  oxide  and  iron  carbides 
in  approximately  equal  proportions.  When  steam  was  passed  over 
this  substance  at  400°  C.,  a  gas  was  obtained  containing  96  per  cent 
of  hydrogen  and  4  per  cent  of  methane.  Over  iron  (reduced  from  the 
oxalate  spread  over  pumice)  at  1250°  C.  was  passed  a  mixture  of  2 
volumes  of  carbon  dioxide  and  1  volume  of  hydrogen.  The  issuing 
gas,  besides  23  per  cent  of  carbon  monoxide  and  76  per  cent  of  hydro- 
gen, contained  0.15  per  cent  methane. 

Messerschmitt  {  recommends  as  a  contact  material  a  mixture  of 
spongy  iron  and  manganese,  cobalt  or  nickel.  The  mixture  may 
be  made  by  adding  the  other  metal  to  the  spongy  iron  and  is  used  in 
powder  form  or  molded  into  briquettes,  or  natural  ores  containing 
these  metals  may  be  used.  This  mixture  has  the  advantage  of  not  being 
easily  poisoned  and  may  be  worked  at  a  lower  temperature.  Man- 
ganese is  of  special  value  if  a  gas  containing  carbon  is  used  in  the  reduc- 
tion stage,  for  manganese  dioxide  in  the  presence  of  carbon,  oxidizes 
the  latter.  Superheated  steam  is  passed  through  the  reduced  mass 
and  generates  hydrogen.  § 

One  form  of  the  apparatus  is  shown  in  Fig.  8 la. 

A  shaft  furnace  for  production  of  hydrogen  from  iron  and  steam  is  described  by 
Messerschmitt  1 1  in  which  the  annular  reaction  chamber  is  divided  into  sections  by 
vertical  projections  from  the  walls  or  by  partitions. 

*  British  Patent  401,  Jan.  6,  1911. 

t  Compt.  rend.  (1910),  151,  355. 

t  U.  S.  Patent  No.  1,109,448,  Sept.  1, 1914;  J.  S.  C.  I.,  1914,  962;  see  also  French  Patent 
No.  461,480,  1913;  J.  S.  C.  I.,  1914,  201. 

§  See  also  U.  S.  Patent  No.  1,152,197,  Aug.  31,  1915;  British  Patent  No.  12,117,  1912; 
J.  S.  C.  I.,  1912,  1079;  German  Patent  No.  291,603,  Aug.  7,  1913;  Chem.  Abs.,  1917,  983. 

||  German  Patent  No.  291,902,  Feb.  12,  1914;  J.  S.  C.  I.,  1916,  927;  Chem.  Aba.,  1917, 
1892. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS    503 

Another  method  by  which  Messerschmitt  *  generates  hydrogen  Is  as  follows: 
The  charge  of  the  reaction  chamber  consists  of  spongy  iron  supported  on  and  mixed 
with  compact  iron.  See  Fig.  816.  The  supports  may  consist  of  plates,  grids  or 
screens  of  iron,  upon  which  is  placed  iron  ore  or  similar  material  mixed  with  short 
iron  bars  or  other  pieces  of  iron.  The  charge  thus  consists  of  alternate  layers  of 
compact  iron  and  spongy  iron.  In  case  of  melting  of  the  spongy  iron  the  spaces 
still  kept  open  for  the  flow  of  gas  and  when  it  becomes  necessary  to  remove  the 
charge,  each  plate  of  iron  carrying  the  spongy  iron  can  readily  be  removed. 

In  another  modification,  Messerschmitt  f  arranges  the  material  in  an  annular 
space  bounded  externally  by  a  refractory  furnace  wall  and  internally  by  a  refractory 
core  or  checker-work  contained  in  an  iron  cylinder.  By  having  the  reaction  mass 
arranged  in  a  narrow  annular  column  around  a  central  combustion  chamber.  J 
With  a  given  lateral  thickness  of  material  in  the  column,  the  ratio  between  heat- 


Gas  Afr 


FIG.  81a. 


FIG.  816. 


absorbing  retort  surface  and  quantity  of  material  is  the  same  whatever  the  dimen- 
sions of  the  apparatus.  Using  relatively  thin  layers  of  reaction  material,  a  uniform 
circulation  of  the  various  gases  through  the  material  is  attained  more  readily  than 
with  a  retort  of  large  cross-section  and  on  account  of  the  combustion  chamber  being 
within  the  reaction  chamber,  heat  radiation  losses  are  minimized.  Fig.  81c  indi- 
cates the  form  of  apparatus  used. 

An  elaborated  form  of  Messerschmitt  apparatus  is  shown  in  Fig.  81d.  § 
A  pair  of  concentric  cylinders,  each  open  at  one  end,  are  arranged  in 

*U.  S.  Patent  No.  1,109,447,  Sept.  1,  1914,  J.  S.  C.  I.,  1914,  962. 

f  British  Patent  No.  18,942,  Aug.  20,  1913;  U.  S.  Patent  No.  1,152,196,  Aug.  31,  1915; 
J.  S.  C.  I.,  1914,  593. 

J  Messerschmitt,  U.  S.  Patent  No.  1,225,263,  May  8,  1917;  Chem.  Abs.,  1917,  2142 
See  also  German  Patent  No.  268,339,  of  1912;  J.  S.  C.  I.,  1914,  137;  1917,  595. 

§U.  S.  Patent  Nos.  1,225,262  and  1,225,264,  May  8,  1917;  Chem.  Abs.,  1917,  2141; 
J.  S.  C.  I.,  1917,  595;  French  Patent  No.  441,015,  1912. 


504 


THE  HYDROGENATION  OF  OILS 


the  furnace  chamber.  The  ring-shaped  space  formed  between  the  two 
cylinders  serves  to  receive  the  ferrous  charge.  The  furnace  space 
surrounding  the  outer  cylinder  and  that  inclosed  by  the  inner  cylinder, 
are  provided  with  brickwork  checkers. 

Messerschmitt  *  subjects  the  reaction  mass  to  combined  external  and  internal 
heating  in  a  modification  of  the  furnace  above  described.  Messerschmitt  f  also 
uses  a  reducing  gas  comprising  a  mixture  of  air  and  gas  produced  out  of  contact  with 
the  reaction  mass  and  partly  burnt.  |  Messerschmitt  §  in  still  another  process  pro- 
duces hydrogen  by  the  alternate  reduction  and  oxidation  of  iron  ores,  etc.,  from 
iron  by  means  of  reducing  gases  and  steam.  The  heating  is  effected  by  a  gas  of  low 
calorific  power,  and  the  reduction  by  a  gas  of  high  calorific  power. 

Nailer  and  Noding  ||  describe  the  following  process  of  generating  hydrogen- 


FIG.  81c. 


FIG.  Sid. 


Steam  free  from  air  is  superheated  to  about  1000°  and  passed  successively  over 
copper  and  iron,  in  a  retort  heated  to  about  800°  C.  To  regenerate  the  metals  from 
the  oxides  produced,  the  undecomposed  steam  from  the  retort  is  converted  into 
water-gas,  which  is  passed  first  over  the  copper  oxide.  The  gases  from  the  retort 
are  led  again  into  the  water-gas  generator  to  reduce  carbon  dioxide  to  monoxide 
and  this  circulation  is  continued  until  the  reduction  of  the  metal  oxides  is  complete 
and  carbon  dioxide  is  no  longer  formed,  whereupon  steam  is  again  led  through  the 
retort  to  produce  hydrogen.  Since  one  volume  of  carbon  dioxide  yields  two  volumes 
of  monoxide,  the  water-gas  generator  is  provided  with  a  valve  by  means  of  which 
certain  proportion  of  the  gas  can  be  withdrawn  to  be  used  as  fuel.  Naher  and 

*  British  Patent  No.  17,692,  Aug.  1,  1913;   Chem.  Abs.,  1915,  359. 
t  British  patent  17,691,  Aug.  1,  1913;    J.'S.  C.  I.,  1914,  593. 
J  See  French  Patent  No.  461,624,  of  1913;  J.  S.  C.  I.,  1914,  313. 
§  British  Patent  No.  17,690,  Aug.  1,  1913;   Chem.  Abs.,  1915,  359. 
||  German  Patent  No.  279,726,  Aug.  7,  1913;  J.  S.  C.  I.,  1915,  355. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS     505 


Noding  *  in  carrying  out  this  process  heat  the  metals  to  at  least  400°  C.  and  the 
steam  to  at  least  200°  C.  The  metallic  oxides  produced  are  again  reduced  to  metal 
at  a  temperature  of  at  least  400°  C.  In  the  production  of  the  reducing  gases,  coal, 
wood  charcoal,  metallurgical  coke,  gas  coke,  or  soot,  may  be  used  as  source  of  carbon, 
and  small  quantities  of  air,  carbon  dioxide,  producer  gas,  water  gas,  or  illuminating 
gas  may  be  added  to  the  steam;  the  reducing  gases  are  produced  at  a  temperature 
of  at  least  400°  C. 

In  connection  with  their  process  of  producing  hydrogen  from  steam  and  iron  cut- 
tings, Naher  and  Noding  f  prepare  cuttings  by  turning  from  cast  iron  with  a  steel 
tool  held  at  an  obtuse  angle  to  the  surface  of  the  cast  iron.  In  this  way  amorphous 
iron  is  obtained,  consisting  of  thin,  overlapping,  very  small  flakes,  which  offer  great 
surface  for  the  action  of  the  steam.  Retorts  charged  with  this  form  of  iron  may 
be  more  quickly  heated  and  less  free  space  is  left  between  the  particles  of  the  charge, 
than  is  the  case  with  other  forms  of  charge.  About  six  times  more  iron  may  be 
charged  into  the  same  space  by  using  this  product,  and  correspondingly  more  hydro- 


;3teoim 


FIG.  Sle. 

gen  is  generated.  Furthermore,  the  charge  retains  its  form  for  at  last  a  week,  at 
1000°.  The  furnace  is  heated  by  oil  and  the  water  gas  or  generator  gas  is  gene- 
rated at  a  high  temperature. 

Naher  and  Noding  J  construct  apparatus  for  the  production  of  hydrogen  from 
iron  and  steam  by  arranging  a  number  of  interchangeable  cylindrical  iron  retorts 
around  a  tar-oil  flame,  in  a  cylindrical  furnace.  The  waste  gases  are  discharged  at 
the  bottom  of  the  furnace  to  avoid  losses  of  the  atomized  oil.  Gas  can  be  generated 
after  an  hour's  heating. 

Spitzer  §  uses  producer  gas  to  heat  iron  oxide  in  a  generator  and  then 
reduces  the  iron  material  with  water  gas.  The  producer  gas  is  mixed 
with  an  excess  of  air  which  tends  to  remove  sulphur  and  carbon  from 
the  spongy  iron.  The  same  apparatus  is  used  to  generate  both  the 

*  German  Patent  No.  286,960,  June  13,  1914.  Addition  to  German  Patent  No. 
279,726;  J.  S.  C.  I.,  1916,  177. 

t  German  Patent  No.  289,207;  Chem.  Abs.,  1916,  2508;  J.  S.  C.  I.,  1916,  538. 

J  German  Patent  No.  290,657,  Dec.  1,  1914;  J.  S.  C.  I.,  1916,  602. 

§U.  S.  Patent  No.  1,118,595,  Nov.  24,  1914;  see  British  Patent  No.  6,155,  of  1014; 
Chem.  Abs.,  1914,  920,  and  1915,  29. 


506 


THE  HYDROGENATION  OF  OILS 


producer  gas  and  water  gas.  After  the  iron  is  reduced  superheated 
steam  is  passed  through  the  mass  and  hydrogen  produced.  The  waste 
gases  are  used  to  superheat  the  steam.  In  Fig.  Sle  a  gas  producer  is 
shown  on  the  right  and  an  ore  chamber  on  the  left.  Intermediate  these 
two  shafts  is  a  purifier  which  is  adapted  to  hold  back  dust  carried  by 
the  gases  coming  from  the  producer. 

Schaef er  *  produces  hydrogen  from  steam  in  an  apparatus  which  con- 
sists of  a  core  of  coarse  material  such  as  iron  bars,  stones,  etc.,  while 
the  outer  portion  of  the  contact  substance  consists  of  finer  pieces  of 


Oois 


Air- 


Steam 


FIG.  81/. 

iron.     It  is  claimed  that  by  this  method  a   more   equal   distribution 
of  heat  is  obtained  than  would  be  were  all  the  particles  of  the  same  size. 

Fig.  8 1/  is  a  view  of  the  hydrogen  generator,  b  and  61  being  the  coarse  and  fine 
iron  material  respectively.  A  layer  of  stones,  a  and  ab  are  placed  at  the  top  and 
bottom  to  better  utilize  the  heat  generated  and  to  give  an  advantageous  control 
over  the  reactions  which  take  place. 

Schaefer  f  observes  that  the  combustion  of  gas  of  high  calorific 
value  must  take  place  with  an  excess  of  air,  in  order  to  avoid  serious 

*  U.  S.  Patent  No.  1,144,730,  June  29,  1915;  British  Patent  No.  16,140,  1914;  Chem. 
Abs.,  1916,  98;  German  Patent  No.  291,022,  July  15,  1913;  J.  S.  C.  I.,  1915,  834;  Chem. 
Abs.,  1917,  873. 

tU.  S.  Patent  No.  1,172,908,  Feb.  22,  1916. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS    507 

drawbacks.  If  such  a  heating  gas,  for  instance  water  gas,  is  burnt 
for  the  direct  heating  of  iron,  with  only  the  quantity  of  air  theoretically 
sufficient,  local  superheating  is  easily  produced  in  the  gas  generator, 
which  results  in  a  sintering  of  the  pieces  of  iron  with  which  the  flame 
first  comes  into  contact. 

According  to  Schaefer,  for  the  purpose  of  avoiding  the  drawbacks  in  question, 
the  gas  of  great  heating  power  is  burnt,  during  the  first  heating  of  the  iron,  with  an 
excess  of  air  as  to  insure  a  perfectly  uniform  heating  of  the  iron  charge.  As  the 
heating  gas,  water  gas  is  employed,  this  requiring  for  its  complete  combustion  2.4 
times  its  volume  of  air.  If,  however,  water  gas  is  burned  in  the  generator  and  this 
proportion  of  air  is  exactly  maintained,  Schaefer  states  that  local  superheating  results, 
with  the  adverse  consequences  above  described.  If  on  the  other  hand  an  excess  of 
about  25  per  cent  over  the  theoretically  correct  quantity  of  air  is  used,  i.e.,  3  cubic 
meters  of  air  to  1  cubic  meter  of  water  gas,  local  superheating  is  stated  to  be  avoided 
and  the  charge  of  iron  is  heated  in  a  uniform  manner. 

A  hydrogen  generator  described  by  Schaefer  *  is  provided  at  the  bottom  with  a 
conical  grate  below  which  is  a  closed  heating  chamber.  A  larger  number  of 
nozzles  or  slits  can  be  obtained  with  a  conical  than  with  a  flat  grate,  thus  ensuring 
finer  division  of  the  hot  gases.  The  emptying  of  the  shaft  is  also  easier  as  the  conical 
grate  guides  the  material  to  the  lateral  outlets.  Schaefferf  states  that  in  an  installa- 
tion for  the  production  of  hydrogen  by  the  treatment  of  iron  alternately  with  steam 
and  with  a  reducing  gas  previously  cooled  and  purified,  the  capacity  of  the  apparatus 
in  which  the  reducing  gas  is  produced  and  of  the  cooler  and  purifier  connected  there- 
with, should  be  so  adjusted  that  the  gas  may  be  supplied  direct  to  the  hydrogen- 
producing  apparatus,  the  working  pressure  being  regulated  according  to  the  vary- 
ing back  pressure  in  the  section  of  the  plant  in  which  hydrogen  is  generated  and  puri- 
fied. One  or  more  elastic  gasholders,  placed  underground,  are  interposed  between 
the  hydrogen  generator  and  the  compressing  apparatus  to  receive  excess  of  hydrogen 
and  supply  it  to  the  compressing  apparatus  when  the  output  of  the  hydrogen  gene- 
rator is  curtailed. 

Dempster  t  produces  hydrogen  by  the  action  of  steam  on  oxidizable  material, 
with  alternate  reduction  by  a  current  of  reducing  gas  (water  gas).  A  pressure- 
regulating  device  is  provided  to  prevent  leakage  of  reducing  gas  into  the  hydrogen 
or  steam  connections,  by  ensuring  a  higher  pressure  in  these  than  in  the  reducing 
gas  mains.  A  vessel  is  divided  into  two  intercommunicating  compartments  which 
contain  water;  one  compartment  is  in  connection  with  the  water-gas  inlet  main 
and  is  provided  with  an  overflow  passage,  while,  in  the  other  compartment,  water 
forms  a  seal  between  the  hydrogen  outlet  main  and  the  hydrogen  scrubber.  Any 
increase  of  pressure  in  the  water-gas  inlet  main,  acting  upon  the  surface  of  the  water 
in  the  first  compartment,  increases  the  depth  of  seal  in  the  second  compartment 
and  necessitates  therefore  a  corresponding  increase  of  pressure  in  the  hydrogen  outlet 
main,  and  in  the  supply  of  steam. 

R.  and  J.  Dempster,  Ltd.  (Manchester,  England),  furnish  hydrogen- 
ating  equipment  similar  to  that  shown  in  Fig.  810.  The  plant  con- 

*  German  Patent  No.  290,529,  May  3,  1914;  J.  S.  C.  I.,  1916,  602. 
t  J.  S.  C.  I.,  1916,  538;  German  Patent  No.  289,208,  April  1,  1914. 
t  British  Patent  No.  16,893,  July  16, 1914  £j.  S.  C.  I.,  1914,  1046;  Chem.  Abs.,  1916,  258. 


508 


THE  HYDROGENATION  OF  OILS 


sists  of  a  blue  water-gas  equipment,  water-gas  holder,  rotary  exhauster, 
steam  engine  and  purifiers,  a  hydrogen  bench  (generators)  hydrogen 
scrubber  and  purifiers  and  a  hydrogen  holder.  Steam  of  60  to  80  Ib. 
pressure  is  used.  The  retorts  of  the  hydrogen  bench  are  heated  by 
means  of  the  blow  gases  of  the  water-gas  generator.  The  author  is 
advised  that  the  cost  of  hydrogen  of  98  to  99  per  cent  purity  is  about 
75  to  90  cents  per  1000  cubic  feet,  with  coke  at  $3.75  per  ton. 

The  disintegration  of  iron  ore  caused  by  the  manner  of  charging  it  into  the  retorts 
(where  it  is  subjected  alternately  to  the  action  of  reducing  gases  and  steam)  is  claimed 
by  Dempster*  to  be  obviated  by  providing  the  retort  with  a  perforated  platform  or 


-To  Wafer  Gas  Holder 


To  Hydrogen  Holder- 


(  )*»-* 

jperheater 

N       >v    / 

l 

l 

~^*  rm^ 

cocoo 

f         \ 

'[    Generator.     1 

'     !!! 

!  ! 

ccccc 

Hydrogen  Bench 

ocooc 

O 

V    ) 

1 

coocc 

'"-Chlmr 

- 

!i 

Hoist 


!  !  1 


FIG. 


plate,  which  is  mounted  on  a  vertical  shaft  and  can  be  raised  and  lowered  from  top 
to  bottom  of  the  retort  for  charging  and  discharging.  The  movement  is  guided 
by  projections  on  the  internal  walls  of  the  retort,  and  the  platform  can  be  revolved 
as  well  as  moved  vertically. 

A  method  for  the  treatment  and  utilization  of  gases  supplied  to  the  furnaces  of 
hydrogen  retorts  is  described  by  Ballingall  (R.  and  J.  Dempster,  Ltd.)f  according 
to  which,  spent  water  gas  from  a  hydrogen-retort  plant  is  preheated  in  a  regenerator 
and  passed  through  the  reaction  zone  of  a  gas  producer.  The  dissociated  gas  is 
burnt  together  with  producer  gas  in  the  region  of  the  retorts  with  a  deficiency  of  air 
so  as  to  form  a  reducing  atmosphere  at  that  point.  On  leaving  this  region  any 
unburnt  gases  are  consumed  by  a  further  addition  of  air  and  give  up  a  portion  of 

*  British  Patent  No.  104,115,  Aug.  12,  1916. 

f  British  Patent  No.  106,067,  Jan.  6,  1917;  J.  S.  C.  L,  1917,  636. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS    509 

their  heat  to  the  incoming  spent  water  gas  in  a  continuous  counter-current  regen- 
erator. 

Bosch  *  in  the  production  of  hydrogen  from  steam  and  iron  ore  uses 
three  or  more  furnaces.  One  of  these  contains  the  iron,  the  other  two 

are  preheaters. 

The  reducing  gases  are  generated  and  then  passed  through  the  iron  ore  which  is 
partially  reduced,  the  reduction  using  up  part  of  the  gas.  The  waste  gas  is  mixed 
with  air  and  passes  into  the  second  preheater  where  it  is  burned,  thus  heating  the 
furnace.  When  reduction  is  complete,  steam  is  passed  through  the  first  furnace 
where  it  is  superheated  and  then  through  the  reduced  iron  mass  when  hydrogen  is 
generated.  In  the  second  cycle  the  reducing  gas  is  produced  in  the  second  furnace, 
then  passed  through  to  the  iron  ore  and  the  waste  gas  burned  in  the  first  furnace. 


Gas.  AirorSieam 

FIG.  81h. 


. 
\  Gars- 

Gas,  Air  or  Steam 


The  cycle  is  then  complete  and  all  furnaces  are  in  same  state  as  when  the  operation 
was  first  started.     Fig.  8lh  shows  the  three-shaft  furnaces  employed. 

Dicke  f  generates  hydrogen  by  the  action  of  steam  on  scrap  from  the  various 
departments  of  an  iron  and  steel  works,  and  the  resulting  iron  oxide  is  utilized  in  the 
blast-furnace  or  open-hearth  furnace.  The  apparatus  is  constructed  of  a  refractory 
chamber  surrounded  by  a  tight  metal  jacket.  The  chamber  is  divided  into  separate 
compartments  by  refractory  walls.  The  compartments  are  arranged  with  valves, 
etc.,  so  that  they  operate  independent  of  each  other.  They  are  charged  with  iron 
ores  or  scrap  iron  and  operated  in  the  usual  manner,  t  The  apparatus  used  by  Dicke 
is  shown  in  vertical  section  in  Fig.  Sli  and  in  horizontal  cross  section  in  Fig.  81  j. 

According  to  Maxted  and  Ridsdale  §  hydrogen  prepared  by  passing 
steam  over  heated  iron  previously  reduced  from  its  oxide  in  a  current 

*  U.  S.  Patent  No.  1,102,716,  July  7,  1914. 

t  German  Patent  No.  280,964,  Aug.  14,  1913;  Chem.  Abs.,  1915,  1531,  J.  S.  C.  I.,  1915, 
492;  Chem.  Abs.,  1915,  1099;  U.  S.  Patent  No.  1,129,559,  Feb.  23,  1915. 

t  See  British  Patent  No.  29,390,  1913.     French  Patent  No.  465,474,  Nov.  28,  1913. 

§  British  Patent  No.  12,698;  Sept.  4,  1915;  J.  S.  C.  I.,  1916,  1060;  Chem.  Abs.,  1917 
638. 


510 


THE  HYDROGENATION  OF  OILS 


of  water  gas,  or  other  commercial  reducing  gas,  contains  considerable 
quantities  of  carbon  monoxide,  due  to  the  deposition  of  carbon  during 
the  reduction  and  its  subsequent  oxidation,  by  the  steam. 

Hydrogen  free  from  carbon  monoxide  is  obtained  by  employing  for  the  reduction 
of  the  iron  oxide  a  reducing  gas  containing  substantially  more  carbon  dioxide  than 
carbon  monoxide,  a  suitable  ratio  being  2:1.  This  may  be  obtained  by  adding 
carbon  dioxide  to  water  gas,  or  by  suitable  modifications  in  the  manufacture  of  the 
reducing  gas,  but  dilution  of  the  gas  with  nitrogen  (e.g.,  by  partial  combustion  of  the 
gas  with  air)  or  by  steam  must  be  avoided.  The  presence  of  carbon  dioxide  in  the 
reducing  gas  prevents  the  deposition  of  carbon  during  the  reduction  of  the  iron 


FIG.  Sli. 


FIG.  Slj. 


oxide  to  iron,  and,  therefore,  no  carbon  monoxide  is  formed  when  steam  is  passed 
over  the  heated  iron  to  produce  hydrogen.* 

J.  Pintsch  Akt.  Ges.  f  employ  pyrite  cinder  in  the  manufacture  of  hydrogen  from 
steam.  A  ferrous  silicate  is  formed  as  a  result  of  the  reduction  of  the  acid  gangue. 
Such  ferrous  silicate  is  quite  fusible,  acting  as  a  slag  and  the  material  is  rendered 
inactive  by  surface  glazing.  This  disadvantage,  as  well  as  the  stoppage  of  the  gas 
passages  when  basic  ores  containing  limestone  are  used,  is  obviated  by  the  employ- 
ment of  compressed  artificial  stones  of  iron  oxides  or  carbonates  on  the  one  hand, 
and  of  oxides  or  carbonates  of  magnesium,  barium,  strontium  or  calcium-magnesium 
oxides  which  possess  the  requisite  porosity. 

In  a  hydrogen  generator  {  operated  with  iron  as  the  active  material,  water  gas 
and  air  are  conducted  into  a  shaft  filled  with  iron  oxide  to  preheat  and  reduce  the 

*  See  also  Danish  Patent  No.  22,122,  May  7,  1917;  U.  S.  Patent  to  Maxted,  1,253,622, 
Jan.  15,  1918;  Chem.  Abs.,  1917,  2030,  and  2721;  1918,  749. 

t  French  Patent  No.  466,739,  Dec.  30,  1913;  Chem.  Abs.,  1915,  1376. 

j  German  Patent  No.  283,160,  Oct.  31,  1913.  J.  Pintsch,  Akt.-Ges.;  Chem.  Abs., 
1915,  2440. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS    51 1 

oxide,  and  then  steam  is  introduced.  The  water  gas  so  used  is  preheated  in  a  pre- 
heating system  wherein  the  heat  from  the  heating  period  of  the  generator  is  utilized. 

According  to  a  process  of  Soc.  U  Hydrogene  *  the  heating  gases,  before  coming 
in  contact  with  the  ferrous  material,  are  passed  through  a  layer  of  refractory  material 
which  serves  as  a  heat  accumulator.  Any  excess  of  reducing  gases  leaving  the  reac- 
tion chamber  is  burnt  in  a  heat  recuperator,  and  the  heat  utilized  to  preheat  the 
steam  passed  in  during  the  subsequent  oxidizing  stage.  Methods  to  prevent  accumu- 
lation of  oxidizable  impurities  introduced  into  the  ferruginous  mass  by  the  gases 
employed  for  heating  and  reducing  are  also  described,  f 

Jaubert,t  proposes  a  process  in  which  steam  is  decomposed  by  metallic  iron, 
and  the  resulting  iron  oxide  reduced  again  to  the  metal  by  purified  water  gas  (free 
especially  from  sulphur  compounds)  which  effects  the  reduction,  at  a  relatively  low 
temperature,  chiefly  at  the  expense  of  the  carbon  monoxide  present,  so  that  the 
reaction  is  almost  entirely  exothermic.  The  material  to  be  treated  is  contained 
in  a  series  of  (preferably  three)  vertical  retorts,  which  are  provided  with  pipes  at 
either  end;  the  pipes  at  one  end  communicate  through  four-way  taps  with  supplies 
of  steam  or  purified  water  gas,  and  those  at  the  other  end  of  the  retorts  with  the 
hydrogen  receiver  or  with  a  residual  gas  chamber,  from  which  the  spent  reducing 
gas  (still  rich  in  hydrogen)  is  distributed  to  burners  projecting  within  the  masonry 
jackets  of  the  respective  retorts.  Further  external  heating  is  unnecessary. 

Hooton  §  proposes  to  treat  metallic  sulphides  and  sulphide  ores,  espe- 
cially iron  pyrites,  with  steam  at  750°  to  1000°,  the  products  being 
porous  oxides  comparatively  free  from  sulphur,  and  a  mixture  of  hydro- 
gen, sulphur,  water  and  sulphur  dioxide. 

The  hydrogen  is  purified,  the  sulphur  being  separated  during  the  purification. 
The  pyrites  are  fed  into  a  retort  into  which  steam  is  blown.  Sulphur  condenses 
in  the  upper  part  of  the  retort  and  collects  in  a  seal.  The  gaseous  products  pass 
through  a  hot  chamber  containing  bog  iron  ore  or  porous  iron  oxide  obtained  by 
the  operation,  to  induce  reaction  between  hydrogen  sulphide  and  sulphur  dioxide, 
then  through  a  chamber  in  which  sulphur  condenses  in  powder  form,  then  through  a 
cooler  preferably  containing  cold  bog  iron  ore  to  remove  the  last  traces  of  hydrogen 
sulphide  and  finally  through  water  to  remove  any  sulphur  dioxide.  The  steam 
may  be  superheated  electrically.  To  reduce  the  quantity  of  water,  the  gases  may 
be  cooled  quickly  after  leaving  the  retort. 

Hydrogen  gas  or  a  mixture  of  hydrogen  and  carbon  monoxide  is  produced  by 
Tully  ||  in  the  following  manner:  In  the  lower  part  of  a  cylindrical  apparatus  is  a 
combustion  chamber  in  which  a  reducing  gas  is  made  by  blowing  air,  or  air  and 
steam,  into  incandescent  fuel.  This  chamber  extends  upwards  into  a  fuel  supply 
chamber,  which  is  surrounded  at  its  lower  part  by  a  reaction  chamber  containing 
iron  ore  in  direct  communication  with  the  combustion  chamber  by  means  of  holes 
and  passages.  Surrounding  the  upper  part  of  the  fuel  supply  chamber  is  a  steam 
superheating  chamber  through  which  the  oxidized  gases  pass,  and  which  is  pro- 
vided with  a  valve  controlled  outlet.  After  the  iron  ore  has  been  reduced,  the  sup- 

*  J.  S.  C.  I.,  1915,  1054,  French  Patent  No.  474,446,  July  1,  1914. 
t  French  patent  472,373,  May  19,  1914. 

j  French  Patent  No.  476,901,  May  14,  1914;  J.  S.  C.  I.,  1916,  635. 
§  British  Patent  No.  18,007,  July  30,  1914;  Chem.  Abs.,  1916,  327. 
||  British  Patent  No.  16,932,  1915;  J.  S.  C.  I.,  1917,  540. 


512  THE  HYDROGENATION  OF  OILS 

ply  of  reducing  gas  is  cut  off,  the  outlet  pipe  is  closed,  and  steam  is  admitted  through 
a  pipe  at  the  top  of  the  apparatus;  this  passes  through  the  superheater  and  over 
the  iron,  the  hydrogen  being  either  tapped  through  a  pipe  just  below  the  reaction 
chamber  or  passed  through  the  incandescent  fuel  and  led  away  through  a  pipe  at  the 
bottom  of  it.  Steam  or  liquid  hydrocarbon  may  be  injected  directly  into  the  com- 
bustion chamber  at  a  point  situated  between  it  and  the  reaction  chamber.  Air 
may  be  admitted  at  the  bottom  of  the  superheater  to  burn  the  carbon  monoxide, 
and  the  heat  of  combustion  utilized  to  maintain  the  temperature. 

Paraffin  hydrocarbons  may  be  dehydrogenated  by  passage  over  ferric  oxide 
heated  to  580°  to  750°  C.  yielding  olefines,  terpenes  and  aromatic  hydrocarbons 
according  to  Ramage.*  The  ferric  oxide  is  reduced  to  ferrous  oxide,  usually  con- 
taining some  iron.  The  reduced  charge  may  be  regenerated  by  blasting  it  with 
steam  at  about  150°  C.  In  the  course  of  this  regeneration,  hydrogen  is  produced, 
which  Ramage  observes  may  be  collected  and  used  for  hydrogenation  purposes. 

MULTIPLE  RETORT  SYSTEM  f 

The  apparatus  provided  for  operating  this  process  consists  of  a 
combustion  chamber  containing  a  number  of  vertical  retorts,  the 
chamber  being  provided  with  a  gas  producer.  A  combustible  gas  is 
delivered  from  the  producer  and  burned  by  means  of  secondary  air  in 
the  combustion  chamber  around  the  outside  of  the  retorts,  the  products 
of  combustion  passing  away  through  recuperators  to  a  stack.  The 
retorts  are  charged  with  iron  ore  of  proper  grade  and  sufficiently 
porous  in  itself  and  of  proper  sized  lumps  to  allow  of  a  more  or  less  free 
passage  of  gas.  It  is  necessary  that  the  greatest  possible  surface  of  ore 
be  exposed.  In  conjunction  with  the  retort  furnace  a  blue  water-gas 
generator  is  provided  for  the  manufacture  of  the  reducing  medium. 
The  blue  water-gas  generator  consists  of  a  round  shell  lined  with  fire 
brick  in  which  coke  or  hard  coal  is  charged,  and  provided  with  air  blast 
and  steaming  connections.  The  blue  water  gas  is  passed  to  a  holder 
and  from  the  hoMer  to  the  hydrogen  retort  furnace.  In  operation  the 
blue  water-gas  holder  is  filled,  the  hydrogen  retorts  brought  up  to 
heat,  and  by  means  of  suitable  valve  connections  the  steam  and  blue 
water  gas  are  alternately  passed  through  the  retorts,  the  resulting 
hydrogen  passing  to  a  holder  and  the  products  of  combustion  passing  to 
the  atmosphere.  In  practice  the  iron  ore  in  the  retorts  may  be  either 
the  ferric  oxide,  Fe2Oa,  or  the  ferroso-ferric  oxide,  FeaC^.  In  either 
case  the  reduction  will  be  back  to  the  ferrous  oxide,  FeO,  only  a  very 
slight  percentage  if  any  of  the  iron  being  reduced  to  the  metallic  state. 
The  apparatus  lasts  indefinitely  with  the  exception  of  the  fire-clay  lining 
in  the  blue-gas  generator,  which  has  to  be  replaced  occasionally,  and  the 

*  U.  S.  Patent  No.  1,224,787,  May  1,  1917. 

f  Modified  Lane  Process  of  Improved  Equipment  Co.,  New  York  City. 


HYDROGEN  BY  ACTION  OF  STEAM  ON  HEATED  METALS    513 

retorts  in  the  hydrogen  furnace.  These  retorts  are  usually  made  of 
cast  steel,  which  seems  to  be  as  satisfactory  as  any  material  which  has 
been  used.  Cast-iron  retorts  have  been  used  with  more  or  less  success. 
The  destruction  of  the  hydrogen  retorts  appears  to  commence  on  their 
outside  diameter,  working  inward  more  rapidly  than  from  the  inside 
outward.  It  is  obvious  that  they  should  fail  in  this  manner  as  the  com- 
bustion surrounding  the  outside  of  the  retorts  continually  cuts  into 
them,  whereas  absorption  by  ferrous  oxide  of  oxygen  takes  place  more 
rapidly  than  the  absorption  of  oxygen  by  metallic  iron,  and  the  entire 
charge  of  ferrous  oxide  is  changed  to  the  ferric  condition  before  there 
has  been  time  for  the  walls  of  the  retorts  to  be  seriously  attacked  by 
the  oxygen  of  the  steam. 

Bergius  *  describes  a  process  of  continuously  generating  pure  hydrogen  from  iron 
and  water  at  a  low  temperature,  from  200°  to  300°  C.  The  hydrogen  is  collected 
in  the  generator  itself  in  a  high  state  of  compression  and  can  be  charged  direct  into 
cylinders.  An  example  of  his  process  is  as  follows:  50  kilograms  of  iron  shavings  and 
265  kilograms  iron  protoxide  and  50  kilograms  of  water  are  heated  to  300°  C.  in  a 
closed  iron  vessel.  When  the  pressure  reaches  150  atmospheres  the  release  valve 
is  opened  just  enough  to  allow  the  gas  to  escape  as  fast  as  liberated  and  to  thus 
maintain  the  initial  pressure.  From  the  above  charge  1  cubic  meter  of  hydrogen  is 
given  off  the  first  hour.  This  rate  is  maintained  until  about  one-half  the  available 
gas  is  evolved,  then  the  rate  is  somewhat  slower.  Common  salt,  iron  chloride  or 
small  quantities  of  hydrochloric  acid  accelerate  the  reaction,  and,  in  addition,  if 
copper,  nickel,  or  platinum,  etc.,  are  placed  in  the  mass,  the  reaction  is  accelerated 
still  more  and  maintains  its  activity  until  the  iron  is  converted  almost  entirely 
into  Fe3O4. 

One  form  of  generator  consists  of  a  pressure  vessel  within  which  is  a  central 
heating  tube  and  around  the  latter  a  series  of  reaction  tubes,  each  of  which  can  be 
brought  in  turn  below  a  feed  opening  in  the  cover  of  the  pressure  vessel. 

Posen  and  Bergius  f  employ  a  somewhat  similar  method  for  the  production  of 
hydrogen  by  the  action  of  water  on  metals  in  a  closed  vessel.  The  reaction  is 
effected  at  a  temperature  below  the  sintering  point  of  the  metal  or  the  solid  reac- 
tion products,  preferably  below  500°  C.  Pure  hydrogen  is  thus  obtained  in  a 
highly  compressed  condition,  and  the  yield  is  nearly  quantitative.  The  addition 
of  electrolytically  conducting  salts  such  as  sodium  chloride  is  stated  to  be  ad- 
vantageous. 

The  decomposition  of  water  by  incandescent  iron,  as  also  the  reduction  of  the 
resulting  iron  oxides  by  the  reducing  gases  requires  a  certain  temperature  of  the  con- 
tact material,  which  is  usually  maintained  by  the  continued  heating  of  the  furnace 
containing  the  iron  material,  or  by  passing  therethrough  hot  combustion  gases.  As  a 
result  of  the  latter  practice,  the  employment  of  a  highly  heated  gas  may  occasion 

*U.  S.  Patent  No.  1,059,818,  April  22,  1913;  German  Patent  No.  277,501,  Nov.  30, 
1913,  addition  to  German  Patent  No.  254,593;  French  Patent  No.  447,080,  of  1912; 
J.  S.  C.  I.,  1915,  229. 

t  German  Patent  No.  286,961,  Nov.  21,  1913;  addition  to  German  Patent  No.  254,593; 
J.  S.  C.  I.,  1916,  177. 


514  THE  HYDROGENATION  OF  OILS 

caking  of  the  contact  material  with  consequent  loss  of  contact  surface  and  reduction 
in  the  yield  of  hydrogen.  By  a  process  recommended  by  the  Berlin  Anhaltische 
Maschinenbau  Akt.  Ges.*  the  required  temperature  of  the  contact  material  is  main- 
tained by  conducting  air  through  the  mass  between  every  double  period  of  reduction 
and  oxidation.  In  this  way  heating  gas  is  saved,  overheating  of  the  iron  charge 
is  avoided,  the  heating  period  is  materially  shortened,  and  the  capacity  of  the  plant  is 
increased.  The  process  is  dependent  upon  the  observation  that  a  complete  oxida- 
tion of  the  iron  material  by  the  steam  passed  thereover  never  practically  results. 
Always  a  portion  of  iron  is  left  in  the  metallic  state  or  in  a  lower  state  of  oxidation. 
Hence,  after  the  passage  of  the  steam,  a  current  of  air  is  passed  through  the  mass, 
causing  complete  oxidation  of  the  iron  or  of  its  lower  oxides  to  the  higher  oxides, 
with  the  evolution  of  considerable  heat.  The  heat  so  generated  is  claimed  to  be 
sufficient  to  maintain  the  normal  progress  of  the  reactions.  The  initial  heating  of 
the  iron  charge  is  effected  by  the  combustion  of  gases  of  high  calorific  value  with 
excess  air,  while  the  periodic  reheating  is  accomplished  by  the  passage  of  air  alone, 
thereby  preventing  fusion  of  the  iron.  During  the  oxidation  period  the  steam  is 
introduced  highly  superheated,  f 

*  German  Patent  No.  294,039,  May  22,  1913;   Chem.  Abs.,  1918,  410. 

t  See  also  French  Patent  No.  465,575,  Nov.  28,  1913;   Chem.  Abs.,  1914,  3491. 


CHAPTER  XXIV 
ACTION   OF  ACIDS   ON   METALS 

One  of  the  oldest  methods  of  generating  hydrogen  and  one  which  is 
to-day  commonly  used  in  the  laboratory  and  for  the  production  of 
hydrogen  on  the  small  scale  is  that  of  acting  on  metals  with  acids, 
iron  or  zinc  and  sulfuric  acid  being  the  materials  usually  employed. 
The  cost  of  generation  in  this  manner  is  too  high  to  permit  of  large 
scale  operations  except  in  those  cases  where  hydrogen  is  obtained  as 
a  by-product  in  the  preparation  of  metallic  salts.  Accordingly  this 
method  of  hydrogen  generation  will  be  considered  only  very  briefly. 

Carulla  endeavors  to  prepare  alkali  salts,  hydrogen  and  iron  oxide, 
the  gas  being  generated  by  the  action  of  hydrochloric  acid  on  iron. 
Instead  of  using  water  alone  for  the  absorption  of  hydrochloric  acid 
in  the  Le  Blanc  process,  some  or  all  of  the  receivers  or  towers  are 
packed  with  scrap  iron  or  mild  steel,  ferrous  chloride  being  thus  formed 
and  hydrogen  evolved.  The  chloride  is  then  converted,  by  precipita- 
tion, into  iron  oxide  *  and,  since  very  dilute  solutions  are  preferable 
for  this  purpose,  the  absorption  of  the  last  traces  of  hydrochloric 
acid  is  rendered  very  easy  by  this  process,  the  ferrous  liquor  plant 
being  conveniently  placed  at  the  end  of  the  system,  and  hydrochloric 
acid  of  high  strength  being  produced,  if  desired,  in  intermediate  parts 
of  the  plant. 

According  to  Barton  f  dilute  sulfuric  acid  is  allowed  to  act  on  zinc 
and  the  zinc  sulfate  solution  produced  is  filtered  and  mixed  with  a 
solution  of  sodium  carbonate  or  bicarbonate,  thus  giving  a  precipitate 
which  is  separated,  washed  and  dried,  and  sodium  sulfate  which  is 
also  recovered. 

The  insoluble  zinc  precipitate  is  proposed  as  "an  excellent  substitute  for  oxide 
of  zinc  used  in  the  paint  and  rubber  industries."  The  apparatus  claimed  consists 
of  a  generating  vessel,  communicating  with  an  acid  tank  by  a  feed  pipe  and  a  return 
pipe,  and  also  with  a  gasometer  and  a  mixing  tank,  the  latter  receiving  the  zinc 
sulfate  solution  from  the  generator  and  sodium  carbonate  solution  from  another 
vessel  and  communicating,  in  its  turn,  with  a  centrifugal  separating  and  washing 
apparatus.  The  generator  may  be  fitted  with  electrodes  for  the  production  of 
electrical  energy. 

*  e.  g.,  as  in  British  Patent  27,302,  1908;  J.  S.  C.  I.,  1909,  1126. 
t  British  Patent  28,534,  Dec,  8,  1910. 

515 


516  THE  HYDROGENATION  OF  OILS 

An  apparatus  arranged  to  generate  electrical  energy  when  zinc  is  being  dis- 
solved in  sulfuric  acid  to  produce  hydrogen  is  set  forth  by  Eastwick  (British  Patent 
10,228,  April  27,  1911).  The  apparatus,  which  is  intended  specially  for  the  gener- 
ation of  hydrogen  by  the  action  of  zinc  on  dilute  sulfuric  acid,  consists  of  a  gen- 
erating chamber,  with  false  bottom,  on  which  rests  the  metal  to  be  acted  upon, 
and  a  liquid-collecting  chamber  situated  below.  The  acid  is  delivered  by  gravitation 
into  contact  with  the  metal  at  a  point  near  to,  but  above,  the  false  bottom,  and  the 
salt  solution  produced  runs  through  into  the  collecting  chamber.  An  electrode 
may,  if  desired,  be  immersed  in  the  liquid,  within  or  below  the  reaction  chamber,  so 
that  the  apparatus  may  serve  also  as  an  electric  cell.  An  apparatus  described  by 
way  of  example  comprises  superposed  chambers  contained  within  a  single  casing, 
the  uppermost  (containing  zinc)  and  the  intermediate  chamber  being  provided 
with  porous  or  perforated  false  bottoms.  Acid  is  conducted  to  the  first  chamber  by 
a  pipe  which  reaches  down  through  the  upper  layers  of  zinc  into  a  cage  having  lateral 
perforations,  and  any  excess  of  pressure  forces  the  acid  back  in  the  supply  pipe,  but 
the  zinc  sulfate  solution  produced  percolates  into  the  lowermost  chamber.  A  zine 
rod  or  plate,  to  act  as  electrode,  is  placed  above  the  false  bottom  in  the  first  chamber 
and  a  copper  electrode  in  the  intermediate  chamber,  so  that,  with  the  descending 
liquid,  an  electric  cell,  suitable  for  electro-plating  work,  etc.,  is  produced,  this  also 
ensuring  the  decomposition  of  any  free  acid  in  the  spent  liquid. 

Hydrogen  gas  is  obtained  by  Pratis  and  Marengo  *  by  acting  upon 
iron  filings  and  water  by  gradual  additions  of  sulfuric  acid  of  50°  Be., 
equal  parts  by  weight  being  taken  of  each.  The  hydrogen  produced 
is  conducted  first  through  water,  then  through  a  solution  of  a  lead  salt, 
and  through  a  device  containing  diaphragms  of  wire  gauze,  to  a  gasom- 
eter, whence  the  gas  traverses  an  insulating  water  valve,  an  elastic 
chamber  and  a  second  device  similar  to  the  first,  when  it  is  taken  by 
branch  pipes  to  the  place  of  utilization.  The  arrangements  described 
permit  of  the  gas  being  produced  under  considerable  pressure. 

To  overcome  the  difficulties  in  the  way  of  generating  hydrogen  from  sulfuric 
acid  and  iron,  Pratis  and  Marengo  (British  Patent  15,509,  June  29,  1907)  propose 
to  employ  the  following  approximate  proportions,  by  weight: 

Broken  iron,  5  parts;  water,  5  parts;  50°  Be",  sulfuric  acid,  5.8  parts;  these  being 
found  to  produce  a  pasty  non-caking  residue,  easy  to  remove  from  the  apparatus  and 
to  work  up  for  the  manufacture  of  ferrous  sulfate  or  Nordhausen  sulfuric  acid. 

The  apparatus  consists  of  a  generating  cylinder,  fitted  with  a  valve  for  discharg- 
ing the  residue.  The  acid  and  water  are  run  in  on  to  the  charge  of  iron  from  reser- 
voirs at  a  higher  level,  the  supply  valve  being  controlled  by  the  bell  of  the  gas  holder, 
and  is  self-closing  when  the  bell  sinks  below  a  certain  level;  or,  if  the  gas  is  to  be  col- 
lected in  receivers  at  high  pressure,  the  full  charge  of  liquids  may  be  added  at  once. 
Purifiers  are  arranged  between  the  generator  and  gas  holder,  and  an  excessive  rate 
of  generation  is  prevented  by  gas  checks,  which  cause  an  increase  of  pressure  in  the 
generator,  whereby  the  acid  is  driven  back  in  the  supply  pipe  and  the  evolution  of 
gas  diminished. 

*  British  Patent  16,277,  July  22,  1896. 


ACTION  OF  ACIDS  ON  METALS  517 

The  reaction  which  takes  place  in  the  spontaneous  formation  of 
iron  rust, 

C02  -f  H20  +  Fe  +  FeCO3  +  H2 

may  be  accelerated  by  agitation,  etc.,  so  as  to  become  a  practicable 
method  according  to  Bruno  *  for  the  production  of  hydrogen.  Frag- 
ments of  cast  iron  or  steel  or  iron  filings  were  introduced  together 
with  water  into  a  steel  bottle  and  carbon  dioxide  was  passed  in  until 
the  air  was  displaced  and  the  liquid  was  saturated  with  the  gas. 
The  bottle  was  then  closed  by  a  steel  cover,  and  placed  in  an  appa- 
ratus where  it  made  about  2000  revolutions  per  hour.  There  was  no 
appreciable  change  in  the  pressure  inside  the  vessel,  and  after  36  to 
40  hours  the  gas  withdrawn  from  the  bottle  consisted  of  pure  hydro- 
gen. At  the  end  of  20  hours  the  gas  consisted  of  about  two-thirds 
of  hydrogen  and  one-third  of  carbon  dioxide. 

Stuart  f  describes  an  apparatus  for  generating  hydrogen  by  allowing 
acid  to  percolate  through  scrap  iron. 

The  iron  is  contained  in  crates  which  are  spaced  away  from  the  walls  of  the  gene- 
rator.    The  latter  may  be  lined  with  lead,  enamel,  etc.,  to  resist  the  action  of  the 
acid.     A  layer  of  asbestos  which  is  held  between  two 
perforated  discs  is  placed  above  and  below  each  crate. 
The  acid  is  introduced  under  pressure  at  the  top  of  the 
generator  and  percolates  through  the  asbestos  and  then 
through  the  scrap  iron.     This  asbestos  serves  as  a  filter 
for  the  gas  and  for  the  spent  acid.     Two  or  more  crates 
of  iron  scrap  may  be  used  in  each  generator.      Fig.  81/c 
shows  the  construction  of  the  apparatus. 

A  method  of  utilizing  the  acid  values  of  sodium  acid 
sulphate  or  bisulphate  is  recommended  by  Becquevort 
and  Deguide  t  as  follows:  A  solution  of  sodium  bisul- 
phate of  density  20°  Be.  (sp.gr.  1.16)  is  added  to  scrap 
iron  in  a  suitable  tank  and  heated  by  steam  to  90°  C. 
The  liberated  hydrogen  is  washed  and  collected  in  a 
holder.  The  resulting  solution  of  ferrous  and  sodium 
sulphates  is  treated  with  an  excess  of  powdered  lime,  FIG.  81fc. 

producing  a  mixture  of   calcium  sulphate  and  ferrous 

hydroxide,  which  is  aerated  to  convert  the  latter  into  ferric  hydroxide.  The  mass 
is  filter-pressed,  and  the  solution  flowing  away  is  concentrated  to  30°  Bo.  (sp.gr. 
1.26)  and  Glauber's  salt  separated  by  crystallization.  The  material  left  in  the 
filter-press  is  used  as  a  gas-purifying  agent. 

Curran  §  in  discussing  the  electrolytic  generation  of  hydrogen,  states  that  savings 

*Bull.  Soc.  Chim.   (1907),   1,  661. 
t  U.  S.  Patent  No.  1,085,366,  Jan.  27.  1914. 

J  British  Patent  No.  107,807,  July  11,  1916;   J.  S.  C.  I.,  1917,  962;   Chem.  Abs.,  1917, 
2947. 

§  Eng.  Mining  J.,  1917,  158. 


518  THE  HYDROGENATION  OF  OILS 

and  improvements  in  service  of  the  electrolytic  method  over  the  zinc-sulphuric  acid 
method  are  most  marked.  The  operating  cost  of  an  electrolytic  plant  is  one-fifth 
that  of  a  zinc-acid  plant  and  there  are  no  acid-eaten  hydrogen  pipes  or  freeze-ups 
in  winter.  The  most  economical  rate  of  generation  under  the  conditions  employed 
by  Curran  was  at  400  amperes  and  36  volts  with  the  temperature  at  53°.  Caustic 
soda  solution  of  26°  Be.  was  used  as  an  electrolyte.  Equipment  and  layout  of  plants 
are  given. 


CHAPTER  XXV 

MISCELLANEOUS  METHODS   OF  HYDROGEN 
GENERATION 

Much  attention  has  been  given  to  the  production  of  hydrogen  by 
chemicals,  which,  when  added  to  water  or  hydrated  substances,  would 
liberate  hydrogen  freely,  thus  enabling  the  generation  of  hydrogen 
at  any  point  without  the  necessity  of  setting  up  elaborate  apparatus. 
Powdered  aluminium  or  silicon  and  alkali,  "  activated  "  aluminium 
and  water,  ferrosilicon  and  calcium  hydrate,  calcium  hydride  and  the 
like  have  been  proposed  under  various  names  such  as  hydrone,  hydro- 
genite,  the  Hydrik  process,  etc.  Bergius  has  brought  out  a  novel 
process  involving  the  treatment  of  carbon  or  iron  with  water  in  a 
liquid  condition  under  very  high  pressures.  The  following  indicate 
the  principal  developments  in  this  direction. 

Foersterling  and  Philipp  *  generate  hydrogen  by  causing  water,  in 
a  finely-divided  state,  to  react  successively  with  relatively  small 
masses  of  sodium,  separated  from  each  other,  in  the  same  containing 
vessel,  in  such  a  way  that  the  supply  of  hydrogen  is  continuous,  and 
at  a  rate  that  substantially  prevents  a  solution  being  formed.  They 
also  propose  silicides  for  the  generation  of  hydrogen.  f  An  intimate 
mixture  of  equal  parts  by  weight  of  sodium  and  aluminium  silicide 
("  sical  ")  is  prepared  by  heating  the  two  substances  in  a  kneading 
machine  until  all  the  sodium  is  molten;  the  kneading  appliance  is 
then  put  into  operation  and  kept  continuously  rotating  while  the 
mixture  cools  down,  after  which  the  latter  is  transferred  to  a  press 
and  briquetted.  One  kilo  of  the  mixture,  when  acted  on  by  water, 
generates  about  700  liters  of  hydrogen,  the  reaction  being  represented 
by  the  equation, 

Al2Si4  +  8  Na  +  18  H2O  =  A12(OH)6  +  4  NasSiOa  +  15  H2. 


Brindley  and  Bennie  (U.  S.  Patent  943,036,  Sept.  14,  1909)  use  a  mixture  con- 
sisting of  finely-divided  aluminium  and  molten  sodium  hydroxide,  the  proportion 
of  the  latter  being  between  1  and  3  mols.  to  1  mol.  of  aluminium.  Silicon  and  zinc 
may  also  be  added. 

Brindley  (U.  S.  Patent  909,536,  Jan.  12,  1909)  treats  an  alkali  or  alkaline-earth 
metal,  for  example  sodium,  in  a  finely-divided  state,  with  a  crude  hydrocarbon  oil 

*  U.  S.  Patent  883,531,  March  31,  1908. 
t  U.  S.  Patent  977,442,  Dec.  6,  1910. 
519 


520  THE  HYDROGENATION  OF  OILS 

or  similar  substance,  which  will  temporarily  prevent  oxidation  of  the  metal,  and  with 
an  inert  substance  such  as  infusorial  earth,  and  the  mixture  is  compressed  into  tablets 
or  briquettes,  which  when  brought  into  contact  with  water  will  generate  hydrogen. 
In  order  to  increase  the  yield  of  hydrogen,  a  metal  (aluminium,  silicon)  which  forms 
a  hydroxide,  the  hydrogen  of  which  can  be  replaced  by  an  alkali  or  alkaline-earth 
metal,  is  also  incorporated  in  the  mixture. 

Philipp  (U.  S.  Patent  1,041,865,  Oct.  22,  1912)  generates  hydrogen  by  the  action 
of  water  on  a  mixture  of  metallic  sodium  and  aluminium  silicide.  The  action  of 
water  on  this  mixture  does  not  proceed  to  completion,  and  the  method  consists  in 
first  treating  the  mixture  with  water,  and  then  passing  the  hot  hydrogen  and  steam 
through  a  similar  mixture  which  has  previously  been  partially  decomposed  by 
treatment  with  water. 

Jaubert  *  suggests  that  the  hydrogen  evolved  in  such  industrial 
processes  as  the  production  of  electrolytic  soda,  be  collected,  deprived 
of  any  oxygen  present  (as  by  passage  over  red-hot  copper),  dried, 
directed  into  an  iron  tube  charged  with  calcium  in  small  pieces,  and 
heated  for  some  hours  to  redness.  The  dark  grey  calcium  hydride 
thus  obtained  is  preserved  in  closed  vessels.  When  the  hydride  is 
brought  into  contact  with  cold  water,  there  is  a  violent  evolution  of 
hydrogen. 

Bamberger,  Bock  and  Wanz  f  generate  hydrogen  from  calcium 
hydride  which  is  mixed  with  substances  such  as  gypsum,  sodium  bi- 
carbonate, soda-lime  or  boric  acid,  which  contain  water  or  carbonic 
acid,  but  which  react  only  when  heated  to  about  80°  C.,  or  a  higher 
temperature. 

Gases  which  are  prepared  by  the  action  of  a  liquid  upon  a  solid,  for  instance, 
hydrogen  by  the  action  of  water  on  calcium  hydride,  are  obtained  pure  and  free 
from  the  water  vapor  which  is  frequently  generated  by  the  heat  of  the  reaction, 
in  the  following  manner:  The  solid  is  placed  in  a  connected  series  of  separate 
vessels,  or  in  superposed  compartments  of  the  same  vessel,  and  the  liquid  is  ad- 
mitted to  the  first,  or  lowest,  of  the  series.  The  gas  given  off,  along  with  some 
vapor  of  the  liquid,  passes  through  the  next  vessel,  or  compartment,  and  so  through 
the  series  and  leaves  the  last  in  a  dry  condition,  the  water  vapor  having  been  re- 
tained by  the  fresh  material.  When  the  first  vessel  is  exhausted  it  is  recharged 
and  connected  to  the  end  of  the  series,  the  second  vessel  becoming  the  first.  In 
this  way  the  process  becomes  continuous.  J 

Schwarz  §  describes  two  simple  methods  for  preparing  pure  hydro- 
gen gas  and  carbonic  oxide.     On  heating  a  mixture  of  zinc  dust  and 
calcium  hydrate  gradually  in  a  combustion  tube,  a  constant  current 
of  pure  hydrogen  is  liberated  according  to  the  equation, 
Zn  +  CaH2O2  =  ZnO  +  CaO  +  H2. 

*  French  Patent  327,878,  Dec.  31,  1902. 
t  German  Patent  218,257,  March  31,  1908. 
t  Jaubert,  French  Patent  381,605,  Nov.  14,  1907. 
§  Ber.,  19,  1140. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     521 

On  mixing  the  zinc  dust  with  calcium  carbonate  in  molecular  pro- 
portions and  heating  as  before,  pure  carbonic  oxide  gas  is  evolved 
thus : 

Zn  +  CaC03  =  ZnO  +  CaO  +  CO. 

In  both  cases  nearly  theoretical  quantities  of  gas  are  obtained. 

Hydrogen  is  produced  by  the  process  of  Jaubert  *  by  ignition  and 
autocombustion  in  a  closed  generator,  of  a  mixture  consisting  of  an 
excess  of  a  combustible  substance  (metal,  metalloid  or  alloy),  capable 
of  decomposing  steam  at  a  high  temperature,  an  oxidizer  or  other 
substance  to  maintain  the  combustion,  and  a  substance  evolving 
steam  on  heating  (which  is  omitted,  partially  or  wholly,  if  steam  be 
introduced  from  an  external  source). 

Suitable  mixtures,  which  may  be  packed  in  metal  cartridges,  to  be  opened  and 
placed  directly  in  the  generator,  are  the  following :  (a)  Powdered  iron  20  kilos,  slaked 
lime  10,  potassium  perchlorate  6,  (6)  ferrosilicon,  with  75  per  cent  of  silicon,  20, 
litharge  10,  soda-lime,  containing  two-thirds  of  sodium  hydroxide  60;  (c)  ferrosilicon 
20,  powdered  iron  5,  wheat  flour  3,  lime  5,  and  potassium  chlorate  3.  If  the  ingre- 
dient evolving  steam  be  omitted,  the  generator  may  be  surrounded  by  a  water 
jacket,  the  two  vessels  being  connected  so  that  the  necessary  steam  is  supplied  from 
the  latter  by  the  heat  of  the  reaction;  a  pipe  from  the  generator  conveys  the  gas 
either  to  the  exterior  or  through  a  purifying  and  drying  apparatus,  to  be  utilized. 
The  generator  described  is  closed  by  a  heavy  lid  which,  for  safety,  is  held  in  position 
by  its  own  weight. 

The  Hydrogenit  process  of  Jaubert  f  involves  mixing  finely-powdered 
ferrosilicon  with  soda-lime  to  produce  a  grayish  granular  mass  which 
easily  ignites  and  burns  readily  even  with  the  exclusion  of  air,  the 
reaction  being 

Si  +  Ca(OH)22  NaOH  =  Na2Si03CaO  +  2  H2. 

From  3  kilos  of  the  mixture,  which,  by  the  way,  is  stable  at  ordinary 
temperature,  about  1  cubic  meter  of  very  pure  hydrogen  is  obtained. 
The  mixture  is  pressed  to  blocks  and  is  shipped  in  metal  containers 
holding  25  to  50  kilos,  affording  8  to  16  cubic  meters  hydrogen  in 
about  a  ten-minute  period.  The  mixture  is  kindled  by  a  small  amount 
of  ignition  powder  or  quick-match.  Equipments  for  furnishing 
150  cubic  meters  hydrogen  per  hour  have  been  made.  The  gener- 
ators are  arranged  in  pairs,  see  Fig.  82. 

A  case  of  hydrogenit  is  placed  in  each  generator.  The  cover  of  the  generator  is 
put  on  and  clamped  in  place  and  the  mixture  lighted  through  a  closable  opening 
in  the  cover.  The  generators  are  equipped  with  water  jackets  and  the  steam  pro- 
duced by  the  heat  of  the  reaction  is,  towards  the  end  of  the  run,  turned  into  the 

*  French  Patent  427,191,  May  21,  1910. 
t  German  Patent  236,974. 


522 


THE  HYDROGENATION  OF  OILS 


generator,  giving  a  larger  yield  of  hydrogen.     The  gas  is  washed  and  dried.     One 
cubic  meter  of  hydrogen  made  from  Hydrogenit  costs  about  32  to  38  cents.* 

Jaubert  (French  Patent  422,296,  Jan.  14,  1910)  has  described  the  following 
modification  of  the  above.  Metals  such  as  aluminium  or  zinc,  or  their  alloys,  or 
metalloids  such  as  silicon  or  carbon,  or  their  compounds,  e.g.,  ferrosilicon,  when 
mixed  with  alkali  or  alkaline-earth  hydroxides  in  the  form  of  dry  powders,  yield 
mixtures  quite  stable  at  ordinary  temperatures.  If,  however,  reaction  be  induced 
by  local  application  of  heat,  hydrogen  is  evolved  and  sufficient  heat  is  developed 
to  cause  the  propagation  of  the  reaction  throughout  the  mass.  A  suitable  appara- 


FIG.  82. 


tus  consists  of  a  tube  closed  at  one  end  by  a  screw  cap  and  having  near  this  end  an 
opening  (with  a  screw  cap)  through  which  a  quick-match  or  piece  of  hot  iron  may 
be  introduced  to  induce  the  commencement  of  the  reaction.  The  other  end  of  the 
tube  is  formed  by  a  perforated  plate,  through  which  the  hydrogen  evolved  passes 
into  a  chamber  packed  with  filtering  material,  and  thence  into  an  annular  space 
formed  between  the  tube  and  a  jacket  extending  nearly  the  whole  length  of  the  latter. 
The  hydrogen  accumulates  in  this  annular  space  under  pressure,  and  is  withdrawn 
as  required  through  a  suitable  outlet. 

Ferrosilicon  containing  75  per  cent  of  silicon,  when  heated  to  a  very  high  temper- 
ature is  capable  of  decomposing  steam  with  sufficient  evolution  of  heat  to  carry  on 
the  reaction, 

3  FeSi6  +  40  H2O  =  Fe3O4  +  18  SiO2  +  40  H2. 

(Jaubert,  French  Patent  438,021,  March  4,  1911.)  The  reaction  rnay  be  regulated 
by  the  addition  of  lime,  which  has  the  further  advantage  of  forming  an  easily-work- 
able slag.  The  apparatus  comprises  a  refractory  chamber  surrounded  by  a  steam 
coil,  the  delivery  end  of  which  terminates  in  a  series  of  injectors,  which  admit  steam 

*  Zeitsch.f.angew.  Chem.  (1912),  2405. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION    523 

into  the  chamber;  a  feeding  hopper  is  provided  at  the  top  of  the  chamber  and  a  door 
for  the  withdrawal  of  the  slag  at  the  bottom. 

An  alkali  or  alkaline-earth  hydroxide,  or  a  mixture  of  the  two,  is  mixed  with 
charcoal  and  a  finely-divided  metal  or  mixture  of  metals,  and  the  whole  is  heated 
in  a  hermetically-sealed  vessel,  with  the  exclusion  of  air,  and  under  diminished  pres- 
sure. Under  the  action  of  the  metal,  according  to  Hlavati  (German  Patent  250,128, 
Feb.  25,  1911)  the  hydroxide  is  converted  into  oxide,  and  hydrogen  and  carbon 
monoxide  are  formed. 

The  Siemens  &  Schuckert  Company  has  worked  out  a  process  for 
the  production  of  hydrogen  from  the  reaction  between  silicon  and 
caustic  soda  solution.  Formerly  steam  was  employed,  but  now  the 
heat  set  free  during  the  reaction  is  utilized  for  maintaining  the  proper 
conditions.  The  evolution  of  hydrogen  gas  takes  place  when  a  25  per 
cent  solution  of  caustic  soda  acts  on  silicon  introduced  in  small  quan- 
tities. The  capacity  of  a  transportable  plant  is  60  to  120  cubic  meters 
per  hour,  while  stationary  plants  are  built  for  capacities  up  to  300  cubic 
meters  per  hour.  The  process  is  a  neat  one,  but  the  cost  is  about 
18.75  cents  per  cubic  meter.* 

A  somewhat  similar  system  is  used  in  France  under  the  name  of 
the  Silicol  process.  Ferrosilicon  or  other  silicon  alloy  is  treated  with 
freshly-prepared  35  to  40  per  cent  caustic  soda  solution.  The  heat 
of  solution  of  the  alkali  raises  the  temperature  to  60  to  80  degrees  and 
enables  the  reaction  to  progress  rapidly.  Hydrogen  by  this  method 
costs  about  20  cents  per  cubic  meter,  f 

By  the  Hydrik  process  aluminum  powder  is  acted  on  by  caustic 
soda  giving  hydrogen  and  sodium  aluminate,  according  to  the  equa- 
tion, 

2  Al  +  6  NaOH  =  2  Al(ONa)3  +  3  H2. 

Fig.  83  shows  a  gas  generator  for  the  Hydrik  process  with  an  hourly 
capacity  of  10  cubic  meters. 

By  the  addition  of  lime,  or  calcium  compounds  that  form  lime, 
according  to  |  Consortium  fur  Elektro-chem.  Ind.  ges.  m.  b.  H., 
nearly  the  full  theoretical  quantity  of  hydrogen  is  rapidly  liberated 
on  heating  silicon  in  an  aqueous  solution  of  caustic  alkali.  The  process 
may  be  carried  out  in  an  iron  generator  fitted  with  stirrers,  and  in 
British  Patent  11,640,  May  13,  1911,  it  is  stated  that  the  temperature 
necessary  for  the  generation  of  hydrogen  from  silicon  and  caustic 
alkali  solutions  may  be  obtained  by  the  solution  of  the  powdered  alkali 
or  alkali  oxides  in  water,  or  by  the  heat  produced  in  the  chemical 
reaction  between  aluminium  or  aluminium  alloys  and  the  alkali. 

*  Met.  and  Chem.  Eng.  (1911),  157. 

t  See  Zeitech.  f .  angew.  Chem.  (1912),  2405. 

J  British  Patent  21,032,  Sept.  14,  1909. 


524 


THE  HYDROGENATION  OF  OILS 


Jaubert  (French  Patent  430,302,  Aug.  6,  1910)  uses  a  strong  solution  of  a  caustic 
alkali,  or  a  solution  of  sodium  or  potassium  sulfate  containing  such,  which  is  made 
to  act  upon  a  compound  or  alloy  of  silicon  (preferably  ferrosilicon,  manganosilicon 
or  silicospiegel)  in  such  a  way,  that  the  heat  produced  in  preparing  the  alkali  solu- 
tion is  utilized  in  effecting  the  reaction,  no  external  heat  being  required.  The  reac- 
tion takes  place  in  a  generating  vessel,  fitted  with  a  stirring  device  and  surmounted 
by  a  feeding  hopper  containing  the  powdered  alloy;  this  vessel  communicates  both 
with  an  arrangement  for  washing  and  cooling  the  gas  and  with  another  vessel,  also 
provided  with  a  stirrer,  in  which  the  solution  of  caustic  alkali  is  prepared  (e.g.,  by 
dissolving  1  part  by  weight  of  sodium  hydroxide  in  H  to  2  parts  of  water).  The 


FIG.  83. 

water  which  has  served  to  cool  the  gas  in  the  condenser  passes  either  to  the  generator 
or  to  the  dissolving  vessel.  A  strong  solution  of  alkali  being  used,  an  acid  silicate 
is  obtained;  moreover,  non-caustic  residues,  suitable  for  use  in  dyeing  and  bleach- 
ing, are  obtained. 

The  preparation  of  hydrogen  under  pressure  by  the  wet  method  is  detailed  by 
Jaubert  *  as  follows: 

The  reaction  by  which  the  hydrogen  is  produced  is  carried  out  under  a  pressure 
above  the  vapor  pressure  of  water  at  the  temperature  in  question,  the  larger  part 
of  the  heat  produced  is  localized  and  stored  in  the  reacting  liquid,  and  by  preventing 
the  vaporization  of  this  liquid,  dry  hydrogen  is  obtained,  the  speed  of  manufacture 
is  increased,  and  the  amount  of  liquid  necessary  for  the  reaction  diminished.  The 
pressure  is  produced  automatically  by  working  with  an  autoclave  generator,  in  which 
the  hydrogen  produced  is  allowed  to  accumulate.  The  generator  is  a  revolving 
cylinder,  provided  with  an  autoclave  cover,  a  charging  chamber  which  penetrates 
some  distance  into  the  interior  of  the  cylinder  and  a  blow-off  cock,  so  that  complete 
mixing  of  the  reagents  can  be  prevented  before  the  reaction  is  started  and  to  allow 
the  hydrogen  formed  to  be  drawn  off. 

To  obtain  a  rapid  and  constant  evolution  of  hydrogen  by  the  interaction  of  sili- 
con, aluminium  or  alloys  containing  the  same,  with  an  alkali  hydroxide,  Jaubert 
(French  Patent  454,616,  April  30,  1912)  prepares  an  emulsion  of  a  concentrated 

*  French  Patent  433,400,  Oct.  25,  1910. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     525 

solution  of  the  latter  with  a  non-saponifiable  oil  or  grease,  such  as  paraffin,  which 
mixture  is  heated  to  100°  C.,  with  the  elements  or  alloys  named,  in  the  form  of  fine 
powder,  water  being  added  as  fast  as  it  is  decomposed,  and  the  frothy  mass  being 
kept  constantly  agitated.* 

Mauricheau-Beaupre  f  adds  to  fine  aluminium  filings  a  small  pro- 
portion of  mercuric  chloride  and  potassium  cyanide,  which  causes  a 
slight  rise  of  temperature  and  produces  a  coarse  powder,  quite  stable 
if  kept  from  moisture.  This  powder  is  treated  with  water  (about 
1  liter  to  a  kilo)  and  the  rise  of  temperature  which  occurs  as  the 
hydrogen  is  evolved  is  watched,  and  regulated  if  necessary  by  the 
addition  of  more  water  so  that  the  temperature  does  not  rise  above 
70°  C.  At  this  temperature  1  kilo  of  the  powder  is  completely 
oxidized  in  about  two  hours. 

The  advantages  of  this  method  are  that  the  apparatus  needed  is  of  the  simplest 
description,  and  can  be  made  of  almost  any  materials,  as  the  products  are  perfectly 
neutral;  that  the  gas  produced  is  pure;  and  that  a  very  large  volume  is  yielded  by  a 
small  weight  of  volume  of  the  reagent  (1  kilo  yields  1300  liters,  or  1  cubic  decimeter 
1770  liters).  Pure  aluminium  filings  with  1  to  2  per  cent  of  mercuric  chloride  and 
0.5  to  1  per  cent  of  potassium  cyanide  should  be  used.  (French  Patent  392,725, 
July  27,  1908.)  Aluminium  hydroxide  is  obtained  as  a  by-product. 

Chem.  Fabr.  Griesheim-Elektron  {  recommend  a  preparation  con- 
sisting of  finely-divided  aluminium  (98  parts)  mixed  with  small 
quantities  of  mercuric  oxide  (1  part)  and  caustic  soda  (1  part).  On 
treatment  with  water,  hydrogen  is  evolved  steadily  and  uniformly, 
1  to  1.2  cubic  meters  (calculated  at  0°  C.  and  760  mm.)  being 
obtained  from  1  kilo  of  the  product.  The  mass  can  be  kept  un- 
altered for  a  long  time  if  protected  from  moisture,  and  can  be  easily 
transported,  1  kilo  occupying  a  volume  of  only  0.8  liter.  The  cost 
is  about  forty-five  cents  per  cubic  meter. 

In  the  corresponding  British  Patent  3188,  Feb.  9,  1909,  it  is  stated  that  aluminium 
in  a  divided  form,  such  as  filings,  dust,  chips  or  factory  waste,  is  mixed  with  a  small 
quantity  of  a  compound  of  a  metal  such  as  mercury,  which  is  electro-negative  to 
aluminium,  and  with  a  small  quantity  of  an  alkali  or  acid,  or  a  borate,  phosphate  or 
other  soluble  substance.  The  alkali,  etc.,  serves  to  generate  sufficient  hydrogen  to 
reduce  the  mercury  or  other  compound,  which  then  forms  an  electro-chemical  couple 
with  aluminium  and  decomposes  water  until  the  aluminium  is  used  up. 

According  to  Uyeno,§  78  to  98  parts  by  weight  of  aluminium  are 
melted  in  a  crucible  and  a  mixture  of  15  to  1.5  parts  of  zinc  and  7.0  to 

*  See  also  U.  S.  Patents  to  Jaubert:  943,022,  Dec.  14,  1909;   1,029,064,  June 
11,  1912;    1,037,919,  Sept.  10,  1912;   and  1,040,204,  Oct.  1,  1912. 
t  Compt.  rend.  (1908),  147,  310. 
J  German  Patent  229,162,  Jan.  17,  1909. 
§  British  Patent  11,838,  May  18,  1912. 


526 


THE  HYDROGENATION  OF  OILS 


0.5  part  of  tin  are  added  to  the  molten  metal,  after  which  the  alloy 
is  cast  in  the  form  of  a  plate.  For  each  part  of  this  alloy  0.12  to 
0.025  part  of  mercury,  or  a  quantity  of  zinc  or  tin  amalgam  containing 
this  amount  of  mercury,  is  taken  and  amalgamated  with  the  upper 
and  lower  surfaces  of  the  plate  by  rubbing  it  in  with  a  steel  brush. 
The  plate  is  then  heated  to  as  high  a  temperature  as  possible  with- 
out volatilizing  the  mercury,  until  the  alloy  has  become  uniformly 
amalgamated,  whereupon  it  is  ready  for  the  manufacture  of  hydrogen 
by  acting  on  it  with  hot  water. 

When  zinc  dust  is  heated  with  hydrated  lime,  as  previously  stated, 
hydrogen  is  formed  according  to  the  equation, 

Ca02H2  +  Zn  =  ZnO  +  CaO  +  H2. 

On  this  reaction  Majert  and  Richter  *  have  based  a  technical  process 
of  generating  hydrogen,  in  which  they  employ  apparatus  as  shown 
in  Fig.  84.  A  heating  chamber  F  carries  a  series  of  horizontal  tubes 


FIG.  84. 

r,  each  of  which  is  provided  at  one  end  with  a  gas  eduction  pipe  e, 
leading  to  a  water  seal  V,  and  at  the  other  end  with  a  removable  cap. 
Iron  or  carbon  may  be  used  in  place  of  zinc. 

In  the  Lahousse  process  f  coal,  mixed  with  barium  sulfate,  is 
heated  at  a  red  heat  so  as  to  produce  carbon  monoxide  and  barium 
sulfide,  according  to  the  equation, 

BaSO4  +  4  C  =  BaS  +  4  CO. 

The  sulfide  of  barium  produced  is  then  heated  to  redness  in  a  current 
of  steam,  with  re-formation  of  barium  sulfate  and  evolution  of 

hydrogen. 

BaS  +  4  H20  =  BaSO4  +  4  H2. 

*  Brahmer,  Chemie  de  Gase,  101. 

f  French  Patent  361,866,  Oct.  24,  1905. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION    527 


The  regenerated  barium  sulfate  is  ready  for  use  de  novo.  The 
carbon  monoxide  produced  in  the  first  operation  may  be  employed 
for  heating  the  retorts.  Lahousse  also  states  that  sulfate  and  sul- 
fide  of  strontium  may  be  used  in  place  of  the  corresponding  barium 
compounds.* 

The  Bergius  process.  Steam  acts  on  incandescent  carbon  to  pro- 
duce hydrogen  and  carbon  monoxide.  Below  650°  C.  carbon  dioxide 
instead  of  carbon  monoxide  is  formed  to  some  extent  according  to  the 
reaction, 

C  +  2  H2O  =  CO2  +  2  H2. 

Bergius  has  found  that  this  reaction  occurs  al- 
most exclusively  if  water  at  a  temperature  of 
about  300°  C.  is  allowed  to  act  on  carbon  under 
a  pressure  sufficient  to  keep  the  water  in  a  liquid 
state.  The  addition  of  small  amounts  of  thal- 
lium salts  is  beneficial  as  the  reaction  is  there- 
by promoted  through  catalytic  action.  In  order 


FIG.  85. 


FIG.  86. 


to  work  under  the  high  pressures  necessitated  by  these  consider- 
ations Bergius  has  made  use  of  apparatus  as  shown  in  Figs.  85 
and  86. 

The  successful  closure  of  the  reaction  chamber  was  attained  by  the  use  of  a 
tapered  plug  forced  into  a  seat  having  a  taper  of  different  angle  so  that  the  contact 
becomes  a  line  rather  than  a  surface.  (Bergius,  Die  Anwendung  hoher  Drucke  bei 
Chemischen  Vorgangen,  Halle,  1913,  6.)  A  charge  of  say  100  kilos  coke  and  200 

*  First  Addition,  Oct.  28,  1905,  to  French  Patent  361,866, 


528 


THE  HYDROGENATION  OF  OILS 


kilos  water  containing  in  solution  1  kilo  of  thallium  chloride  is  placed  in  a  strong 
iron  vessel  provided  with  a  valve,  and  the  vessel  is  heated  to  340°  C.     (German 
Patent   259,030,   June  24,    1911.)     The 
mixture  of  hydrogen  and  carbon  dioxide 
which  collects  in  the  upper  part  of  the 
vessel  is  blown  off  through  the  valve  at 
intervals  of  half  an  hour,  and  the  carbon 
dioxide  is  absorbed  by  lime. 

Using  iron  instead  of  carbon, 
Bergius  *  has  developed  a  process 
of  making  hydrogen  without  the 
accompanying  formation  of  car- 
bon dioxide,  based  on  the  reaction 
between  iron  or  other  metal  and 
water  at  a  temperature  of  300°  C., 
or  so.f  A  receptacle  as  shown  in 
Fig.  87  is  employed.  This  has  an 

expanded   basal   part   serving   as  

a  reaction   chamber   and  a  long 
tubular  outlet. 


Iron  and  water  (which  should  contain 
an  electrolyte  such  as  sodium  chloride) 
are  placed  in  the  chamber  and  are  heated 
to  300°  C.  The  pressure  rises  to  100 
atmospheres  or  higher.  Water  condenses 
in  the  tubular  outlet  and  flows  back 
into  the  reaction  zone.  Hydrogen  is 
blown  off  by  means  of  the  valve  in  the 
upper  part.  It  is  stated  that  in  this 
way  hydrogen  can  be  obtained  directly 


-a 


FIG.  87. 


*  Bergius  (Zeitsch.  f.  angew.  Chem.  (1913),  517)  states  that  with  his  process 
hydrogen  containing  less  than  1/100  of  a  per  cent  of  impurities  may  be  produced.  In 
apparatus  which  has  been  thoroughly  tested  at  Hanover,  a  vessel  of  a  capacity  of  80 
liters  produced  12  cubic  meters  of  hydrogen  hourly.  Bergius  states  that  the  construc- 
tion of  vessels  of  larger  size  up  to  a  capacity  of  about  one  cubic  meter  offers  no 
difficulty.  In  large  plants  which  are  arranged  for  proper  heat  utilization,  Bergius 
estimates  the  cost  of  hydrogen  at  about  2  cents  per  cubic  meter.  The  advantage 
of  this  process  is  that  very  pure  hydrogen  under  high  pressure  may  be  produced  at 
a  low  cost  and  without  an  expensive  equipment,  enabling  works  requiring  only  a 
small  amount  of  hydrogen  to  produce  this  gas  on  the  spot  at  low  cost.  The  iron 
oxide  formed  by  the  reaction  can  be  reduced  by  heating  with  carbon  at  1000°  C. 
and  is  then  ready  to  be  used  a  second  time. 

t  German  Patent  254,593,  Oct.  24,  1911,  and  German  Patent  262,831,  July  7, 
1912. 

J  Apparatus  fitted  with  an  agitator  and  adapted  for  the  treatment  of  liquids  with 
gas  under  high  pressures  is  described  in  Chem.  Ztg.  (1913),  1288. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION    529 

under  a  pressure  more  than  100  atmospheres.  Lower  oxides  of  metals  may  re- 
place the  metals  themselves.  (French  Patent  447,080,  Aug.  9,  1912.)  The  water 
may  contain  neutral  salts,  acids  or  other  conductive  compounds.  The  reaction 
is  also  accelerated  by  the  use  of  a  second  metal,  such  as  copper,  nickel  or  platinum, 
more  electropositive  than  the  principal  metal.* 

Sabatier  f  produces  a  mixture  of  hydrogen  and  methane  by  passing 
moist  purified  water  gas  over  finely-divided  nickel  at  a  temperature  of 
from  300  to  450°  C.  The  water  gas  is  first  purified  by  removing  carbon 
dioxide  by  means  of  sodium  carbonate  and  caustic  soda  or  potash,  and 
is  then  passed  over  copper  to  remove  sulphur. 

Sabatier  observes  that  the  manufacture  of  methane  or  of  mixtures  of  methane 
and  hydrogen  has  been  carried  out  by  producing  water  gas,  by  depriving  the  gas 
of  carbon  dioxide  with  the  aid  of  an  alkaline  carbonate  and  by  finally  passing  the 
gas  over  heated  nickel.  This  process  has  never  produced  good  practical  results  on 
account  of  the  following  reasons:  The  water  gas  constantly  varies  in  composition 
and  as  the  whole  operation  is  based  on  a  definite  composition  of  the  gas,  the  process 
soon  becomes  defective,  the  production  of  hydrogen  becomes  insufficient,  the  nickel 
is  carbonized  and  after  a  short  time  the  operation  has  to  be  stopped.  The  carbon- 
ized nickel  has  to  be  regenerated  and  an  operation  of  the  kind  requires  time  and 
expense. 

The  Reaction  in  the  Nickel  Tubes.  The  practical  execution  of  this  reaction 
depends  on  the  following  conditions:  1.  The  initial  cleaning  of  the  gas.  2.  The 
arrangement  of  the  apparatus.  3.  The  preparation  of  the  nickel.  4.  The  way  of 
conducting  the  operation. 

1.  The  gas  deprived  of  carbon  dioxide  consists  of  a  mixture  of  carbon  monoxide 
and  hydrogen.  It  must  be  freed  from  traces  of  sulphur  compounds  that  it  may 
contain  and  for  this  purpose  the  gas  is  made  to  pass  through  tubes,  Fig.  87a,  con- 
taining copper  in  the  shape  of  turnings  or  of  a  fine  powder.  These  tubes  are  built 
into  a  water-gas  furnace  and  must  be  maintained  at  a  temperature  between  500° 
and  600°  C.  The  copper  heated  to  dark  red  withholds  any  impurities  that  might 
deteriorate  the  nickel.  After  long  use  the  copper  becomes  partly  transformed  into 
copper  sulphide  and  must  be  renewed.  2.  The  apparatus  for  the  reaction  with 

*  Badische  Anilin  und  Soda  Fabrik.,  French  Patent  441,695,  March  23,  1912. 
Operations  in  which  hydrogen,  or  gases  containing  it,  are  employed  under  pressure 
and  at  a  high  temperature  can  be  carried  out  in  vessels,  provided  with  special  strength- 
ening appliances,  although  the  wall  of  the  interior  vessel  in  which  the  reaction  takes 
place  is  composed  of  some  material,  such  as  iron  free  from  carbon  or  nickel,  which  is  in- 
capable of  offering  by  itself  sufficient  mechanical  resistance  to  the  conditions  imposed 
by  the  process,  but  chemically  is  as  resistant  as  possible  to  hydrogen.  (See  also  U.  S. 
Patent  1,077,034,  Oct.  28,  1913;  and  1,075,085,  Oct.  7,  1913.) 

Hydrogen  under  pressure  may  be  used  in  conjunction  with  vessels  constructed  of 
steel  alloys  at  temperatures  considerably  above  450°  C.  when  these  alloys  contain  certain 
proportions  of  chromium,  vanadium,  tungsten,  molybdenum  or  the  like.  Suitable  alloys 
contain  (1)  tungsten  18  and  chromium  3  per  cent,  and  (2)  chromium  2.9  and  carbon  0.2 
per  cent.  Alloys  containing  too  high  a  percentage  of  nickel  should  be  avoided.  (J.  S. 
C.  I.  (1913),  1010;  Badische  Anilin  und  Soda  Fabrik.,  British  Patent  29,260  and  13,258, 
Dec.  19,  1912,  and  June  7,  1913.) 

t  U.  S.  Patent  No.  956,734,  May  3,  1910. 


Nickel 


VttltV 


530  THE  HYDROGENATION  OF  OILS 

nickel  consists  of  horizontal  metallic  flattened  tubes.  3.  The  nickel  producing  the 
catalytic  reaction  must  be  in  a  powdered  condition  and  is  obtained  by  reducing 
commercial  nickel  oxide.  The  oxide  is  reduced  by  applying  the  mixture  of  carbon 
monoxide  and  hydrogen  that  issues  from  the  copper  tubes.  The  reduction  is  effected 
between  350  and  450°  C.  4.  The  tubes  for  the  nickel  are  grouped  in  several  series 

that  are  independent  of  one  another,  so  that 
one  series  may  be  emptied,  filled  again  and 
reduced  without  interrupting  the  whole 
operation.  5.  The  reaction  with  nickel  is 
effected  at  350°  C.,  but  the  temperature  may 
vary  between  300°  and  450°  C.  without  in- 
volving any  serious  disadvantage.  As  the 
gases  are  moist  when  they  reach  the  nickel 
and  the  reaction  is  accompanied  by  a  con- 
siderable production  of  water,  the  permanent 
formation  of  carbon  on  the  nickel  according 
to  the  reaction  2CO  =  C+CO2  does  not  take 
place. 

Jaubert  *  tests  silicol  (ferro  silicon)  and 
other  silicon  alloys  used  in  the  production  of 
hydrogen,  by  the  following  procedure:  Five 
portions  (10  g.  each)  of  the  ferrosilicon  con- 
tained in  thin  paper  thimbles  are  added  suc- 

FIG.  87a.  cessively  to  50  cc.  of  40  per   cent  sodium 

hydroxide  solution  in  a  2-liter  flask  and  kept 

at  80°  C.  The  evolved  gas  is  led  through  three  wash  bottles  containing,  respec- 
tively, pure  water,  bromine  water  (to  oxidize  hydrogen  phosphide)  and  10  per  cent 
sodium  hydroxide  solution  (to  remove  bromine  vapor).  To  the  last  wash-bottle, 
in  which  a  thermometer  hangs,  is  connected  a  gas  receiver.  The  volume  of  gas 
obtained  is  reduced  to  0°  C.  and  760  mm.  50  g.  of  silicol  yield  70  to  75  liters  of 
hydrogen. 

Baillio  f  produces  hydrogen  and  sodium  silicate  by  the  following 
method.  An  excess  of  silicon  is  repeatedly  acted  on  with  10  per  cent 
caustic  soda  solution,  in  a  closed  vessel  and  the  hydrogen  and  sodium 
silicate  solution  produced  by  each  treatment  are  removed  before  adding 
fresh  caustic  soda  solution. 

De  la  Fresnaye  and  Suchy  {  give  the  following  as  a  cyclic  process  for 
producing  nascent  hydrogen  by  means  of  esters. 

An  ester  is  saponified  with  water,  in  the  presence  of  a  metallic  oxide  or  carbon- 
ate and  the  material  to  be  treated  with  nascent  hydrogen,  to  which  may  be  added  a 
reducing  agent,  such  as  trihydroxybenzene  or  gallic  acid.  For  example,  petro- 
leum containing  sulphur  compounds  is  treated  with  ethyl  acetate,  lead  oxide  or  car- 
bonate, and  a  small  proportion  of  trihydroxybenzene,  the  lead  sulphide  produced 

*Rev.  Gen.  Chim.  pure  et  appl.,  1913,  16,  341;  Chem.  Techn.  Rep.,  1914,  38,  380; 
J.  S.  C.  I.,  1914,  1091. 

t  Chem.  Abs.,  1916,  1582,  J.  S.  C.  I.,  1916,  633.     U.  S.  Patent  No.  1,178,205. 
j  French  Patent  No.  476,454,  Apr.  23,  1914;  J.  S.  C.  I.,  1916,  48. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     531 

is  filtered  off,  and  ethyl  acetate,  which  is  continuously  reformed,  during  the  reaction 
is  recovered  by  fractionating  the  filtered  product;  the  reaction  is  facilitated  by 
adding  ether  to  prevent  emulsification. 

Kessener  *  produces  hydrogen  by  the  following  method:  Waste  liquor  sludges, 
or  the  liquors  themselves  (e.g.,  from  paper  factories),  are  inoculated  with  anaerobic 
bacteria  capable  of  producing  methane  or  hydrogen,  selected  with  special  regard 
to  the  nature  of  the  particular  waste  liquors  employed.  Suitable  nutrient  salts 
are  added  and  the  bacteria  are  grown  under  conditions  which  minimize  the  pro- 
duction of  free  nitrogen. 

In  Snelling's  process  f  hydrogen  is  separated  from  producer  gas  or 
other  gases  by  diffusion  through  porous  earthenware  or  alundum  con- 
tainers having  a  thin  coating  of  platinum  or  palladium.  The  porous 
tube  is  electrically  heated  by  resistance  wires  preferably  to  above 
800°,  the  gas  being  introduced  under  pressure.  Hydrogen  diffuses 
through  the  platinum  or  palladium  film  and  porous  tube  and  is  then 
drawn  off.  Several  other  forms  of  apparatus  are  also  described.  Cobalt, 
nickel  or  iron  may  be  used  instead  of  platinum  or  palladium  but  with 
decreased  efficiency. 

The  separation  of  the  different  components  of  a  gas  mixture  is  brought  about 
by  Wussow  J  by  leading  the  gas  over  the  surface  of  permeable  or  absorbing  media. 
These  media  may  be  either  solid  or  liquid,  and  different  forms  may  be  used  simul- 
taneously to  separate  the  different  constituents  of  a  complex  mixture.  Moving 
permeable  surfaces  may  be  used  to  accelerate  the  diffusion.  The  diffused  gas  may 
be  removed  from  the  farther  side  of  the  diaphragm  by  maintaining  a  low  pressure  or 
by  circulating  an  indifferent  gas,  such  as  steam,  ammonia,  or  carbon  dioxide,  which 
afterwards  can  be  removed  by  solution  or  condensation.  Diffusion  may  also  take 
place  through  several  media  in  succession,  each  of  which  causes  a  partial  separation. 
As  an  example  of  the  process,  using  a  layer  of  water  as  permeable  medium,  at 
0°  C.,  this  would  absorb  85.2  times  as  much  carbon  dioxide  as  hydrogen,  and  at 
20°  C.,  49  times  as  much.  A  system  has  been  devised  on  this  principle  for  the 
manufacture  of  hydrogen  from  water  gas  at  a  cost  of  3.0  Pf.  per  cubic  meter. 
A  product  containing  99  per  cent  hydrogen  can  be  prepared  at  a  cost  of  6.4  Pf.  per 
cubic  meter. 

Currne  §  provides  a  method  for  the  separation  of  various  gases  in  a 
gaseous  mixture  containing  acetylene,  ethylene,  methane  and  hydrogen 
with  traces  of  other  gaseous  substances,  such  as  impurities,  whereby 
the  available  gases  are  separated  one  from  another  in  a  form  and 
condition  in  which  they  are  available  for  commercial  use. 

In  carrying  out  the  process,  an  apparatus  as  shown  in  Fig.  876  is  filled  with  char- 
coal and  connected  with  the  container  in  which  the  body  of  gas  is  stored.  The  upper 

*  German  Patent  No.  290,126,  Feb.  7,  1914;  J.  S.  C.  I.,  1916,  486. 

t  U.  S.  Patent  No.  1,174,631;  Chem.  Abs.,  1916,  1424,  J.  S.  C.  I.,  1916,  527. 

t  German  Patent  No.  295,463,  Apr.  15,  1913;  J.  S.  C.  I.,  1917,  330. 

§  U.  S.  Patent  No.  1,181,116,  May  2,  1916;  J.  S.  C.  I.,  1916,  683. 


532 


THE  HYDROGENATION  OF  OILS 


pipes  are  connected  to  the  receivers  arranged  to  receive  tne  respective  gases.  The 
charcoal,  having  an  affinity  for  the  acetylene  and  ethylene,  is  stated  to  take  up  or 
absorb  these  gases,  while  hydrogen  and  other  gases  pass  through  the  vessel  unchanged. 
This  operation  continues  until  the  charcoal  has  taken  up  all  of  the  acetylene  and 
ethylene  gases,  which  such  a  quantity  of  charcoal  is  capable  of  containing.  Heat 
is  then  applied  to  the  vessel,  raising  its  temperature  to  around  200°  C.,  at  which 
temperature  all  of  the  acetylene  and  ethylene  contained  in  the 
charcoal  will  be  driven  out.  When  these  gases  have  been  com- 
pletely expelled  from  the  charcoal  the  latter  is  cooled  and  is  ready 
for  another  operation.  The  hydrogen  obtained  is  claimed  to  be  free 
from  all  impurities  of  the  type  known  as  catalytic  "  poisons  "  so 
that  it  is  considered  especially  well  adapted  for  use  in  catalytic 
hydrogenation  processes. 

Scholl  *  produces  a  mixture  of  nitrogen  and  hydrogen  in  which 
the  ratio  of  nitrogen  to  hydrogen  is  equal  to  R,  by  mixing  ammonia 
gas  and  air  in  the  proportion  of  (2R  -f-  4  to  3R—  1)  and  passing  the 
mixture  over  a  catalytic  agent  to  induce  dissociation  of  the  ammonia 
and  combination  of  the  oxygen  with  hydrogen.  For  example,  a 
mixture  of  equal  parts  of  nitrogen  and  hydrogen  is  obtained  by 
charging  a  closed  vessel  with  ammonia  gas  under  pressure,  intro- 
ducing air  until  the  total  pressure  is  four  times  the  absolute  pressure 
of  the  ammonia,  and  then  passing  the  mixture  over  a  catalytic  agent. 
t  An  apparatus  is  described  by  Oyobigawa  f  whereby  air-free 

FIG.  876.       hydrogen  may  be  generated  from  the  start,  the  waste  solution  may 
be  discharged  without  admission  of  air,  and   the   quantity  of  solid 
reagent  may  be  regulated  to  control  the  pressure  and  volume  of  the  gas. 

The  method  of  Quentin  and  Guillien  {  depends  upon  the  decomposition  of  water 
by  fused  zinc,  the  bath  of  zinc  being  kept  molten  by  the  combustion  of  a  portion  of  the 
gas  produced  by  the  reaction.  The  apparatus  consists  of  a  bath  for  the  molten 
zinc,  in  which  is  a  perforated  steam-coil  connected  with  an  outer  coil  heated  by  a 
burner.  At  the  top  of  the  bath  an  inclined  surface  is  fixed,  which  carries  the  zinc 
oxide  away  as  it  forms. 

A  method  for  preparing  hydrogen  is  described  by  Helbig  §  which  is  based  on  the 
reaction  of  aluminum  with  caustic  soda;  810  g.  aluminum  and  3600  g.  caustic  soda 
are  required  to  furnish  one  cubic  meter  of  hydrogen.  Inasmuch  as  commercial 
aluminum  and  caustic  soda  may  be  regarded  as  99  and  77  per  cent  pure,  respectively, 
5485  g.  of  the  latter  would  be  required  to  furnish  1000  1.  of  hydrogen  gas.  Helbig 
notes  that  this  yield  constitutes  a  saving  of  20  per  cent  as  compared  with  the  usual 
method  based  on  the  reaction  of  iron  and  sulphuric  acid. 

Activation  of  the  aluminum  is  secured  under  the  influence  of  heat,  which  brings 
about  a  considerable  increase  in  the  yield  of  hydrogen  obtained  when  the  product 
is  subsequently  treated  with  water.  1 1 

The  activation  of  the  aluminum  results  from  the  surface  amalgamation  of  the 
metal,  principally  upon  the  production  of  the  amalgam  by  the  reduction  of  the 

*  U.  S.  Patent  No.  1,123,394,  Jan.  5,  1915;  J.  S.  C.  I.,  1915,  228. 
t  Japanese  Patent  No.  29,910,  August  18,  1916;   Chem.  Abs.,  1917,  412. 
J  French  Patent  No.  476,994,  May  18,  1914;   J.  S.  C.  I.,  1916,  601. 
§Ph.  praxis;   through  Boll.  chim.  farm,  53,  71,  1914;  Chem.  Abs.,  1915,  1373. 
||  German  Patent  No.  294,910,  Jan.  27,  1916;  L.  Elkan  Erben  G.m.b.H.,  J.  S.  C.  I., 
1916,  386;   Chem.  Abs.,  1918,  605. 


MISCELLANEOUS  METHODS  OF  HYDBOGEN  GENERATION     533 

mercury  compound,  and  from  the  etching  action  of  caustic  soda.  The  amount 
of  hydrogen  evolved  is  claimed  to  be  greatly  increased  if  the  activation  is  effected 
in  whole  or  in  part  with  heating,  either  amalgamating  the  aluminum  with  heating, 
or  etching  with  caustic  soda  in  the  heat,  or  canning  out  the  whole  process  at  an 
elevated  temperature.  In  the  subsequent  evolution  of  hydrogen  the  use  of  hot 
water  is  not  then  necessary,  e.g.,  50  g.  aluminum  filings  are  heated  on  the  sand  bath 
in  a  dish  for  about  thirty  minutes  at  180°,  and  then  sprinkled  with  1  per  cent  mer- 
curic chloride  solution.  The  excess  is  poured  off  and  washed  with  pure  alcohol. 
After  drying  0.2  g.  of  the  product  are  drenched  with  about  10  cc.  of  a  1  per  cent 
caustic  soda  solution  which,  after  a  short  time,  is  made  up  to  1  1.  with  pure  water. 
In  twenty-five  minutes  about  40  cc.  hydrogen  are  evolved.  Without  previous 
heating  of  the  aluminum,  only  31  cc.  hydrogen  are  evolved  under  otherwise  like 
conditions. 

According  to  Hamlin  *  balloons  are  generally  inflated  with  hydrogen  from  scrap 
iron  and  hot  acid,  unless  there  is  some  other  source  of  the  gas  close  at  hand.  The 
French  army  has  made  use  of  processes  which  would  be  far  too  expensive  for  most 
commercial  purposes,  but  which  have  the  advantage  of  requiring  none  but  readily 
portable  materials  and  apparatus,  f  Simple  apparatus  designed  by  Jaubert  for  the 
decomposition  of  "  hydrolith,"  which  is  essentially  calcium  hydride  with  some 
calcium  oxide  and  nitride,  yields  1  cubic  meter  of  hydrogen  per  kilogram  of 
hydrolith.  Jaubert's  process  involving  the  treatment  of  ferro-silicon  or  mangano- 
silicon  with  water  and  caustic  soda  appears  to  be  a  reaction  difficult  to  control. 
Jaubert  has,  therefore,  introduced  another  "  hydrogenite  "  process.  Ferro-silicon 
is  intimately  mixed  with  dry  caustic  soda  and  quicklime,  and  the  bricks  obtained 
are  sealed  in  tin  cases  to  keep  out  moisture.  When  wanted,  the  brick  is  placed 
within  a  water-jacketed  apparatus,  and  a  hot  wire  is  forced  into  the  brick.  The 
mass  burns  without  giving  any  flame,  some  steam  is  generated  in  the  jacket,  and 
this  steam  enters  the  brick  and  hastens  the  liberation  of  hydrogen.  The  ferro- 
silicon  used  is  of  a  very  high  grade,  containing  more  than  90  per  cent  of  silicon.  The 
reactions  give  hydrogen,  lime  and  sodium  silicate;  the  iron  is  unessential,  and  is 
used  only  because  it  is  cheaper  to  manufacture  rich  ferro-silicon  than  to  isolate  silicon 
itself. 

Fourniols  {  gives  a  review  of  the  methods  that  have  been  proposed 
for  the  commercial  production  of  hydrogen.  The  hydrogenite,  hydro- 
lith, and  silicol  processes  are  discussed  at  some  length  with  reference 
to  apparatus  for  field  use. 

He  states  that  the  problem  of  transportation  presents  the  greatest  difficulties  in 
connection  with  the  utilization  of  the  hydrogen  gas  set  free  in  large  quantities  as  a 
by-product  in  electrolytic  caustic  and  chlorine  plants.  In  transporting  this  hydrogen 
the  great  weight  of  the  cylinders  which  must  be  moved  to  get  a  small  amount  of 
hydrogen  to  a  certain  point  was  a  serious  obstacle.  This  gave  rise  to  the  develop- 
ment of  the  other  processes  above  mentioned  involving  the  use  of  portable  generating 
apparatus.  A  comparison  of  the  price  of  transportation  in  this  way  with  the  com- 
pressed hydrogen  method  is  given  as  follows: 

*  J.  Ind.  and  Eng.  Chem.,  1915,  542. 

t  Engineering,  99,  1915,  415. 

j  Rev.  gen.  sci.,  1915,  26,  339;   Chem.  Abs.,  1915,  2294. 


534  THE  HYDROGENATION  OF  OILS 

Cylinders  with  Compressed  Hydrogen  Hudrolith 

Francs  Francs 

8000  tubes  at  80  fr 640,000  48  tons  at  5  fr.  per  kg 240,000 

50,000  cubic  meters  of  hydrogen  Apparatus  for  generating 40,000 

at  0.40  fr 20,000 

Carriers  for  tubes 60,000  Carriers  for  reagents 4,000 

12  carriages  of  3  tons 240,000  2  carriages  of  3  tons 40,000 

960,000  324,000 

This  table  is  only  intended  to  compare  transportation  cost.  The  hydrolith  process 
is  expensive  as  a  stationary  means  of  production.  Fourniols  states  that  the  latest 
German  process  for  both  lighting  and  inflating  purposes,  using  coke  and  oil,  is  also 
capable  of  being  transported  ready  for  generating  purposes. 

Barnitz  has  reviewed  the  field  of  hydrogen  prod  uction  and  utilization  in  Metallur- 
gical and  Chemical  Engineering,  April  1,  1916  and  Journal  of  the  Aeronautical 
Society  of  America,  May-June,  1916.  In  the  first-mentioned  paper  the  Linde 
process,  iron  and  steam  method,  hydrogen  by  the  decomposition  of  hydrocarbons 
and  by  electrolytic  methods  are  considered.  The  application  of  hydrogen  in  the 
hydrogenation  of  fatty  oils  is  briefly  discussed.  Modern  methods  of  manufacture 
of  hydrogen  are  outlined  by  Gas  World,  1918,  68,  4.  In  the  report  of  the  British 
Comptroller  and  Auditor  General,  it  is  stated,  that  the  cost  of  hydrogen  gas  showed 
an  increase  from  $4.60  per  1000  cu.  ft.  in  1912-13  to  $5.25  in  1913-14.*  The  output 
during  the  latter  year  was  2,023,607  cu.  ft.  as  compared  with  3,493,296  cu.  ft.  in 
1912-13.  Seeker  f  outlines  the  methods  in  use  for  the  commercial  production  of 
hydrogen  and  the  manner  in  which  the  gas  is  employed  for  industrial  purposes. 
The  generation  of  hydrogen  by  different  methods  and  the  cost  of  equipment  is  dis- 
cussed by  Bontoux.  |  A  review  of  the  developments  in  hydrogen  gas  manufacture 
during  1914  appears  in  Zeitsch.  angew.  Chem.,  Aufsatzteil,  1915,  221.  Sander  § 
gives  a  review  of  the  principal  processes  for  the  manufacture  of  hydrogen  on 
the  large  scale  for  military  purposes;  and  of  the  methods  for  handling  the  gas 
in  the  field.  A  review  of  the  subject  of  the  application  of  hydrogen  gas  in 
aeronautics  is  given  by  Redgrove.  ||  The  production  of  hydrogen  by  the  electrical 
decomposition  of  acetylene,  the  use  of  hydrolith,  hydrogenite  and  the  like  are 
discussed.  The  manufacture  of  hydrogen  for  military  purposes  is  ably  described 
by  Ardery.  T[ 

Crossley**  discusses  at  length  the  methods  of  manufacture  of  hydro- 
gen and  its  uses.  A  review  of  modern  apparatus  for  the  preparation 
of  hydrogen  is  given  by  Kausch.ff 

Teissier  and  Chaillaux  JJ  heat  a  mixture  of  barium  sulphate  and 

*  J.  Gas  Lighting,  129,  1915,  442. 

tPolytech.  England,  1914,  61,  66;   Chem.  Abs.,  1914,  3619. 

J  Matieres  Grasses,  1914,  4194;   Seifen.  Ztg.,  1914,  987. 

§  Chem.  Abs.,  1916,  808,  J.  Gasbel,  1915,  637. 

||  Chem.  Trade  J.,  60,  359;  Chem.  Abs.,  1917,  2264. 

1  Trans.  Am.  Electrochem.  Soc.,  1916,  29,  549;   Met.  Chem.  Eng.,  1916,  14,  333. 

**J.  S.  C.  I.,  1914,  1135. 

ft  Berlin  Chem.  App.,  1915,  2,  125  and  141. 

it  French  Patent  No.  447,688,  1912;   J.  S.  C.  I.,  1913,  234  and  1914,  1137. 


MISCELLANEOUS  METHODS  OF  HYDROGEN  GENERATION     535 

manganous  oxide  to  a  red  heat,  finally  to  a  white  heat,  and  pass  steam 
under  pressure  over  the  resulting  mass,  when  the  following  reactions  are 
stated  to  take  place: 

BaSO4 + 4MnO  =  BaS +4Mn02, 

BaS+4MnO2  =  BaS+4MnO+2O2, 
BaS +4MnO  +4H  2O  =  BaSO4 +4MnO  +4H ,. 


CHAPTER  XXVI 

HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 

The  production  of  hydrogen  and  oxygen  by  the  electrolysis  of 
water,  though  one  of  the  oldest  electrochemical  experiments,  and 
proposed  in  a  large  number  of  patents,  in  the  past  has  been  carried 
out  industrially  only  to  a  limited  extent.  There  was  considerable 
difficulty  in  developing  the  laboratory  apparatus  so  that  it  would 
operate  successfully  in  practice,  one  of  the  hardest  conditions  to  meet 
being  the  necessity  of  absolute  safety  of  operation,  and  this  required 
the  exclusion  of  every  possibility  of  the  formation  of  an  explosive  gas 
mixture.  Another  difficult  matter  was  the  requirement  of  providing  a 
material  for  the  electrodes,  which  was  not  at  all  or  only  slightly  attacked 
by  the  electrolyte,  and  the  necessity  of  constructing  apparatus  with 
a  small  internal  resistance.* 

These  problems  appear  now  to  have  been  worked  out  satisfactorily 
so  that  large  scale  electrolysis  of  water  is  on  a  solid  industrial  basis. 
The  principal  processes  or  systems  used  in  practice  include  those 
of  the  International  Oxygen  Co.,  Garuti,  Schoop,  Siemens-Halske, 
Schmidt,  Schuckert  and  Burdett.f 

*  The  Electrolysis  of  Water,  Richards  and  Landis,  Trans.  Am.  Electrochem. 
Soc.,  Ill,  104,  and  IV,  112,  is  concerned  largely  with  the  theory  of  the  subject,  while 
a  paper  by  Richards  bearing  the  same  title,  appearing  in  the  Journal  of  the  Franklin 
Institute,  1905,  377,  treats  of  practical  developments  in  hydrogen  and  oxygen  gener- 
ation. 

t  In  the  electrolysis  of  water  there  are  certain  constants  whose  values  are  the 
same  under  all  conditions  of  operation  within  certain  limits.  The  first  constant 
is  the  amount  of  hydrogen  liberated  per  ampere  hour  of  current  passed  through  the 
cell  generator;  the  figure  is  0.03738  gram  or  0.014825  cubic  foot  of  hydrogen  gas 
measured  at  0  degree  and  760  mm.  pressure.  Thus,  at  400  amperes,  which  is  the 
customary  operating  amperage  for  most  cell  generators,  the  production  will  be  5.93 
cubic  feet  of  hydrogen  and  2.96  cubic  feet  of  oxygen  (at  0  degree  and  760  mm.  pres- 
sure) per  hour.  At  20  degrees  and  760  mm.  pressure  the  output  will  be  6.36  cubic 
feet  of  hydrogen  and  3.16  cubic  feet  of  oxygen  per  hour  per  cell  generator.  The 
second  constant  is  the  minimum  voltage  that  will  force  the  current  through  the  cell 
generators.  For  a  solution  of  sodium  hydroxide  in  water  the  minimum  voltage  is 
1.69  volts,  for  potassium  hydroxide  1.67  volts;  this,  then,  is  the  lowest  voltage  at 
which  decomposition  of  water,  or  electrolysis,  takes  place.  In  order  to  produce 
gas  with  current  at  this  voltage,  the  cell  generator  would  have  to  be  constructed 
in  such  a  manner  as  to  do  away  with  all  internal  electrical  resistance  which  is  obvi- 
ously impossible  and  so  the  operative  or  practical  voltage  is  higher  than  the  theoret- 
ical. With  a  current  of  400  amperes  the  voltage  will  vary  from  1.9  to  4,  depending 

536 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER  537 

D'Arsonval,  in  1885,  was  perhaps  the  first  to  install  a  plant  for 
furnishing  oxygen  electrically  in  the  laboratory.  He  used  30  per 
cent  caustic  soda  solution  as  electrolyte,  cylindrical  sheet-iron  elec- 
trodes, a  current  density  of  two  amperes  per  square  decimeter,  and 
enclosed  the  anode  in  a  woolen  bag,  to  serve  as  a  diaphragm.  Only 
the  oxygen  was  saved.  The  apparatus  used  sixty  amperes,  furnisheci 
some  100  to  150  liters  of  oxygen  daily,  and  was  in  use  several  years. 

Latchinoff  used  an  asbestos  cloth  partition,  ten  per  cent  caustic 
soda  solution,  iron  electrodes,  3.5  amperes  per  square  decimeter 
and  2.5  volts  working  tension;  or  with  a  five  to  fifteen  per  cent  sul- 
furic  acid  solution  he  used  lead  anodes  and  carbon  cathodes.  In 
his  first  apparatus,  Figs.  88  and  89,  the  units  were  all  in  parallel,  but 
afterwards  he  used  series  electrodes,  the  one  side  of  an  electrode 
acting  as  an  anode  and  the  other  as  a  cathode;  a  series  of  forty  was 

on  the  type  of  cell  generator.  With  the  first  constant  given  the  amount  of  hydrogen 
produced  per  400  amperes  per  hour  and  the  minimum  or  theoretical  voltage  given 
it  is  a  simple  matter  to  determine  the  yield  of  gas  per  kilowatt-hour  of  electricity 
used.  The  theoretical  efficiency  will  be  400  amperes  X  1.69  volts  or  0.67G  kilowatt- 
hour  to  produce  6.36  cubic  feet  of  hydrogen.  The  theoretical  yield  per  kilowatt- 
hour  per  cell  generator  will  be  9.408  cubic  feet  of  hydrogen.  In  practice  the  yield 
is  from  4.5  to  8.25  cubic  feet  of  hydrogen  per  kilowatt-hour. 

In  general,  electrolytic  plants  consist  of  the  following  important  parts,  cell  gener- 
ators for  producing  the  gases,  a  motor-generator  set  to  deliver  a  direct  current  at 
the  proper  potential  or  voltage,  gasometers  and  storage  tanks  for  storing  the  gas 
as  it  is  generated  and  compressors  and  compressor  motors  for  raising  the  pressure 
of  the  gas  to  the  required  point.  Stripped  of  everything  but  essentials  the  compo- 
nent parts  of  all  cell  generators  are:  a  container  tank  for  holding  the  solution;  one 
or  more  positive  electrodes,  one  or  more  negative  electrodes,  immersed  in  the  solu- 
tion; means  for  separating  the  electrodes  to  prevent  mixture  of  gas  and  means  for 
separately  collecting  the  gas  as  it  is  generated.  The  separating  medium  is  usually 
a  diaphragm  and  may  be  of  metal,  earthenware  or  cloth.  The  diaphragm  may  be 
a  conductor  or  non-conductor  of  electricity  and  if  of  conductive  material  it  should 
be  insulated  from  the  electrodes.  The  effect  of  the  diaphragm  is  to  divide  the 
generator  into  two  or  more  partitions,  and  the  gases  as  generated  will  rise  to  the  top 
of  the  partition,  there  to  be  drawn  off  by  means  of  pipes  which  lead  to  header  pipes 
connecting  a  line  of  cell  generators,  each  gas,  of  course,  being  drawn  off  by  means 
of  separate  pipe  lines.  The  header  pipes  in  turn  are  connected  to  a  main  gas  line 
which  leads  the  gases  to  their  respective  gasometers.  From  the  gasometers  the 
gas  is  drawn  off  by  means  of  compressors  and  compressed  into  storage  tanks  for  use. 

The  majority  of  installations  require  a  motor-generator  set  to  obtain  the  required 
voltage  for  operating.  The  current  must  be  direct.  The  motor-generator  set 
should  be  heavily  built  in  order  to  operate  on  a  twenty-four  hour  load.  The  com- 
pressors employed  are  specially  adapted  for  handling  these  gases.  The  size  and 
character  of  the  gasometers  used,  of  course,  depends  on  the  size  of  the  installation. 

Below  is  given  a  typical  operating  cost  of  an  electrolytic  plant  consisting  of 
100  cell  generators  with  a  production  capacity  of  632  cubic  feet  of  hydrogen  and  316 
cubic  feet  of  oxygen  in  one  hour  and  15,168  cubic  feet  of  hydrogen  and  7584  cubic 


538 


THE  HYDROGENATION  OF  OILS 


FIG.  88. 


FIG.  89. 


feet  of  oxygen  in  24  hours.     The  yearly  production,  300  days  24  hours  per  day,  is 
4,550,400  cubic  feet  of  hydrogen  and  2,275,200  cubic  feet  of  oxygen. 

Each  cell  generator  requires  about  2  volts  at  400  amperes  equivalent  to  800  watts 
or  0.8  kilowatt-hour. 

100  cells  X  0.8  K.W.H.  X  24  hours  X  300  days  =  576,000  K.W.H.  yearly  plus 
25  per  cent  for  loss  through  motor-generator  set  =  720,000  K.W.H.  yearly. 
Hydrogen  compression  requires  4  K.W.H.  per  hour. 
4  K.W.H.  X  24  hours  X  300  days  =  28,800  K.W.H.  yearly. 

(Compression  to  300  pounds  per  square  inch.) 
Oxygen  compression  requires  12  K.W.H.  per  hour. 
12  K.W.H.  X  24  hours  X  300  days  =  86,400  K.W.H.  yearly. 

(Compression  to  1800  pounds  per  square  inch.) 
Current  consumption  yearly: 

Cell  generators 720,000 

Hydrogen  compression 28,800 

Oxygen  compression 86,400 

Total 835,200 

Fixed  charges: 

Depreciation,  maintenance,  yearly $3000 . 00 

Interest  on  investment . 1500 . 00 

Labor: 

300  days,  24  hours,  at  30  cents  per  hour $2160.00 

With  current  at  a  price  of  say  1  cent  per  kw.-hour,  which  although  a  low  rate  is 
not  excessively  low  for  this  class  of  service,  the  total  operating  cost  will  be  $15,012.00 
per  year. 

The  demand  for  oxygen  in  metal  working  lines  is  at  present  so  great  and  so  poorly 
met  that  in  the  majority  of  cases  the  oxygen  produced  by  an  electrolytic  plant  may 
be  disposed  of  under  contract  at  such  terms  as  will  result  in  the  hydrogen  being 
produced  at  a  relatively  low  cost. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


539 


used  on  a  normal  lighting  circuit,  with  current  density  of  ten  amperes 
per  square  decimeter,  and  parchment  partitions  between  the  electrodes 
to  separate  the  gases.  Latchinoff  was  also  the  first  to  carry  out  the 
decomposition  under  pressure,  using  a  strong  iron  vessel  as  elec- 
trolyzer,  and  by  an  ingenious  system  of  floating  valves  keeping  the 
pressure  of  the  two  gases  equal  in  the  apparatus.  Fig.  90  shows  this 
apparatus,  the  action  of  which  will  be  evident  from  a  short  inspec- 
tion. 

Renard's  apparatus  for  the  generation  of  hydrogen  is  shown  in 
Fig.  91.     The  container  is  made  of  cast  iron  and  serves  as  the  nega- 


FIG.  91. 


tive  electrode.  The  cylinder  C  of  asbestos  material  encloses  the 
positive  electrode  which  is  cylindrical  in  shape  and  is  made  either  of 
iron  or  nickel.  Through  the  bottom  of  the  diaphragm  cylinder  the 
U-tube  R  establishes  communication  between  the  inner  and  outer 
vessels.  The  electrolyte  is  a  solution  made  by  dissolving  15  parts 


540 


THE  HYDROGENATION  OF  OILS 


FIG.  92. 


FIG.  93. 


FIG.  94. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


541 


of  caustic  soda  in  100  parts  of  water.  Before  the  gases  are  passed 
to  the  gas  holder  they  are  led  through  the  pressure  equalizer  marked 
H  and  0.  With  a  current  of  25  amperes  at  3.5  volts  a  yield  of  12 
liters  of  hydrogen  and  6  liters  of  oxygen  per  hour  is  obtained. 

A  form  of  construction  of  the 
Renard  *  type  is  shown  in  Fig.  92 
and  also  in  Fig.  93. 

The  multiple  cell  of  Schmidt  f 
looks  somewhat  like  a  filter  press, 
Fig.  94,  and  consists  essentially  of 
bipolar,  iron  electrodes,  connected 
in  series.  Each  frame  in  the  press 
contains  an  iron  electrode,  which 
acts  as  a  double-pole  (bipolar)  elec- 
trode, sheets  of  asbestos  cloth  held 
between  the  frames  acting  as  par- 
titions, reinforced  with  rubber  on 
the  edges  for  making  tight  joints. 
The  electrolyte  is  a  ten  per  cent 
solution  of  potassium  carbonate, 
filled  into  the  apparatus  through  the 
standpipe  on  the  right,  which  com- 
municates with  all  the  compartments 
through  holes  in  the  frames  similar 
to  the  usual  filter-press  construction. 
The  gases  evolved  escape  by  similar 
passages  into  the  cylinders  on  the  left 
end,  where  they  separate  from  the 
electrolyte  and  pass  upwards,  while 

the  electrolyte,  dragged  by  the  gas  bubbles,  flows  downwards  back 
into  the  apparatus,  thus  maintaining  an  efficient  circulation.  With 
forty  plates  about  2.5  volts  are  absorbed  in  each  cell,  using  a  current 
density  of  about  two  amperes  per  square  decimeter. % 

The  apparatus  is  shown  in  detail  in  Fig.  95.  A  110- volt  direct- 
current  lighting  circuit  may  be  employed  for  the  operation  of  a  series 
type  apparatus  composed  of  the  requisite  number  of  cells.  The  press 

*  Delmard,  German  Patent  58,282,  Nov.  23,  1890. 

t  German  Patent  111,131,  June  13,  1899. 

t  A  multiple-cell  generator  of  the  filter  press  type  is  manufactured  by  Shriver  & 
Co.,  Harrison,  N.  J. 

A  filter-press  type  of  hydrogen  generator  having  an  output  of  16  cu.  m.  of  hydrogen 
per  hour  is  made  by  Maschinenfabrik  Surth,  G.m.b.h.  Siirth  am  Rhein  bei  Koln. 


FIG.  95. 


542 


THE  HYDROGENATION  OF  OILS 


I 
I 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


543 


has  to  be  taken  apart  and  cleaned  every  six  weeks  and  the  asbestos 
diaphragms  have  to  be  renewed  from  time  to  time. 


FIG.  98. 


FIG.  99. 


Schoop,  in  1900,  devised  an  apparatus  with  non-conducting  and 
non-porous  partitions,  which  has  gone  into  considerable  commercial 
use.  Fig.  97  shows  the  section  of  the  apparatus,  where  aa  are  the 


544 


THE  HYDROGENATION  OF  OILS 


tubular  electrodes  of  sheet  hard  lead,  enclosed  by  glass  or  clay  sus- 
pen4ed  tubes  c,  which  are  perforated  at  their  lower  end;  the  electrode 
surface  is  further  increased  by  fine  hard  lead  or  iron  wires  hung  inside 
the  tubular  electrodes,  the  latter  being  perforated  above  the  level 
of  the  electrolyte  in  order  to  let  the  internally-generated  gas  escape. 
Each  cylinder  contains  two  anodes  and  two  cathodes.  When  alkaline 
electrolytes  are  used  and  iron  electrodes,  the  working  voltage  is  2.25; 
when  sulfuric  acid  of  density  1.235  is  used,  with  hard-lead  electrodes, 
the  working  voltage  is  3.6  to  3.9.  Fig.  98  shows  a  single  electrode  and 
Fig.  99  an  installation  of  the  Schoop  system.* 


-T>    -fa 


FIG.  100. 


-t   -fa 


M 


N 


FIG.  101. 


c 

M 

K 

FIG.  102. 

Garuti,  in  1892,  introduced  a  new  electrolytic  principle  into  these 
apparatus  for  the  decomposition  of  water.  He  used  a  nearly  com- 
plete metallic  partition  between  the  electrodes,  and  avoided  the  evolu- 
tion of  gases  on  this  partition  by  keeping  the  working  voltage  between 
the  electrodes  below  three  volts.  A  metallic  partition  can  only  act  as 
an  intermediate  or  bipolar  electrode  by  virtue  of  the  current  entering 
and  leaving  it;  but  this  would  make  two  decompositions  between 

*  Schoop  (Zeits.  Elektrotechn.  Wien  (1900),  18,  441)  discusses  the  difficulties 
met  with  in  the  construction  of  a  suitable  apparatus  for  the  technical  electrolytic 
manufacture  of  hydrogen  and  oxygen,  and  gives  a  description  of  patents  dealing 
with  this  subject.  In  the  Schoop  apparatus  it  is  claimed  that  1.5  cubic  meters 
of  hydrogen  and  oxygen  are  produced  per  11  horse-power  hours.  Richards  (Jour. 
Franklin  Inst.  (1905),  390)  notes  that  the  output  is  given  as  68  liters  of  oxygen  and 
136  liters  of  hydrogen  per  electrical  horse-power  hour.  A  description  of  the  Schoop 
system  is  given  in  the  Centralblatt  f.  Accum.,  Feb.  15,  1903.  It  is  stated  that  the 
length  of  the  tubes  is  chosen  according  to  the  pressure  under  which  the  gases  are 
wanted.  The  following  results  were  obtained  with  the  Schoop  apparatus  during 
one  year:  One  electric  horse-power  hour  gives  97.5  liters  of  hydrogen  and  48.75  oxy- 
gen (probably  under  atmospheric  pressure);  i.e.,  for  one  cubic  meter  of  mixed  gas 
6.8  horse-power  hours  are  required;  with  warm  acid  (sulfuric  acid  of  1.23  specific 
gravity  being  always  used)  this  value  is  reduced  to  6.2  horse-power  hours;  if  the 
price  of  one  horse-power  is  1  cent,  the  cost  of  the  production  of  one  cubic  meter  of 
mixed  gases  is  4.2  to  4.8  cents.  The  purity  of  the  oxygen  is  99  per  cent,  that  of  the 
hydrogen  97.5  to  98  per  cent. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


545 


the  original  electrodes,  necessitating  an  absorption  of  2  X  1.5  =  3 
volts  in  decomposition.  As  long  as  the  working  voltage  is  kept 
below  3,  the  partition  must  act  merely  as  a  partition,  the  same  as  a 
non-conducting  partition.  Reference  to  Figs.  100,  101  and  102  will 
make  this  entirely  clear.  If  2  electrodes  are  placed  in  a  vessel  (Fig.  100) 

containing  acidulated  water  and 
are  separated  by  a  sheet  of  metal 
c  (Fig.  101),  two  separate  decom- 
position chambers  result  and  the 
sheet  metal  serves  as  a  bipolar 
electrode,  so  that  the  side  towards 
the  anode  evolves  hydrogen  and 
that  towards  the  cathode,  oxygen. 
Since  the  1.5  volts  are  required 
for  the  decomposition  of  water, 
the  cells  M  and  N  will  require  3 
volts.  If  the  diaphragm  is  raised 
somewhat  so  the  chambers  M  and 
N  are  in  communication  (Fig.  102) 
the  evolution  of  gas  will  take  place 
only  on  the  terminal  electrodes 
and  not  on  the  intermediate  con- 
ducting septum.  The  latter  be- 
comes a  bipolar  electrode  only 
when  the  electromotive  force  ex- 
ceeds 3  volts.  The  advantage 
gained  by  the  Garuti  process  is 
in  the  simplicity  and  economy  of 
making  the  partitions  of  sheet 
metal  instead  of  burnt  clay,  rubber,  glass,  etc. 

Garuti  devised  many  modifications  in  the  details  of  his  cells,  of 
which  Fig.  103  may  represent  the  most  recent.  The  original  forms 
made  of  sheet  lead  (using  dilute  sulfuric  acid  electrolyte)  got  out 
of  shape  too  easily,  and  were  replaced  by  sheet-iron  apparatus,  using 
caustic  soda  solution.  The  electrodes  are  only  twelve  millimeters  from 
each  other,  and  separated  by  a  sheet-iron  partition  with  small  per- 
forations in  it,  the  latter  allowing  free  passage  of  current  but  being 
too  small  to  allow  any  gas  bubbles  to  pass.  The  alternate  compart- 
ments are  connected  with  oxygen  and  hydrogen  mains,  in  which  are 
enlargements  for  collection  of  spray  and  moisture,  which  runs  back 
into  the  cell.  Current  densities  of  two  to  three  amperes  per  square 
decimeter  are  possible  with  a  working  voltage  between  2.45  and  3, 


FIG.  103. 


546 


THE  HYDROGENATION  OF  OILS 


using  caustic  soda  solution  of  21°  Be.     The  cell  shown  in  Fig.  104  is 
intended  to  take  400  amperes,  and  to  require  one  kilowatt  of  power. 
The  Garuti  type  Cll  generator  consists  of  45  separate  compart- 


FIG.  104. 

ments  made  of  16-gauge  sheet  iron  welded  together  to  form  a  single 
unit.*  The  sides  of  the  compartments  are  used  as  diaphragms  and  are 
usually  perforated  (Fig.  105)  to  allow  circulation  of  the  electrolyte  but 


FIG.  105. 


FIG.  106. 


Perforated  compartment  walls  of  the  Garuti  generator. 

*  In  1892  Garuti  took  out  a  patent  (British  Patent  16,588,  April  25,  1892)  de- 
scribing an  apparatus  consisting  of  a  container  having  an  inverted  leaden  case  with 
partitions  of  sheet  lead  soldered  together  so  as  to  form  a  case  divided  into  parallel 
cells  open  only  to  the  water  at  the  bottom.  The  partitions  of  the  cells  separate  the 
anodes  and  cathodes  which  are  placed  alternately  and  are  insulated  in  the  cells  by 
means  of  combs  made  of  suitable  material.  In  1896  Garuti  and  Pompili  (British 
Patent  23,663,  Oct.  24,  1896)  described  an  improvement  on  the  former  patent, 
involving  the  perforation  of  the  diaphragms  in  their  lower  part  by  small  holes  as 
near  as  possible  to  each  other.  See  also  U.  S.  Patents  to  Garuti  534,259,  Feb.  19, 
1895,  and  Garuti  and  Pompili  629,070,  July  18,  1899. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


547 


not  the  gas.  The  perforations  extend  lengthwise  along  the  lower 
edge  of  each  compartment  wall  3  inches  from  the  bottom,  forming  a 
perforate  strip  2J  inches  wide.  An  electrode 
is  placed  in  each  compartment  and  the  elec- 
trodes are  alternately  positive  and  negative.  All 
like  electrodes  are  connected  together.  Each 
compartment  is  f  inch  in  width  and  30  inches 
long.  The  electrodes  are  insulated  from  the 
compartments  and  are  prevented  from  coming 
in  contact  with  the  walls  by  means  of  small 
porcelain  insulators.  The  gas  from  all  of  the 
FIG.  107.  Compartments  hydrogen-producing  compartments  is  collected 
or'  in  a  gas  bell  welded  to  one  side  of  the  cell  proper 
and  is  led  through  a  water  seal  and  to  a  header  pipe  and  then  to  a 
gasometer.  The  oxygen  gas  is  handled  in  a  like  manner.  The  cells 
as  well  as  the  container  tanks  and  pipe  lines  are  insulated  from  the 
ground.  The  pipe  from  the  cell  to  the  header  pipe  is  insulated  from 
the  latter  by  means  of  a  sleeve  of  rubber  and  glass.* 

Siemens  Bros.  &  Co.  and  Obach  devised  the  apparatus  shown  in 
Fig.  112,  the  principle  being  similar  to  that  of  the  Garuti.  The  cast- 
iron  vessel  a  is  surrounded  by  heat-retaining  material,  in  order  that 
the  temperature  of  the  cell  may  be  automatically  raised  and  thus  its 
running  resistance  lowered.  A  cylindrical  iron  anode  /  is  separated 
from  the  encircling  cathode  g  by  a  cylinder  of  wire  netting  c,  held 
in  place  by  the  porcelain  block  k.  The  electrolyte  is  dilute  caustic 
soda;  the  gases  escape  above  from  the  spaces  n  and  m.  The  whole 

*  When  the  Garuti  cell  is  first  installed  the  efficiency  will  often  be  as  high  as 
6  cubic  feet  or  so  of  hydrogen  per  kw.-hour,  but  the  depreciation  is  said  to  be  perhaps 
more  rapid  than  in  some  other  types  of  generators  and  in  time  the  hydrogen  output 
may  drop  to  about  5  cubic  feet.  Thus  under  the  normal  operating  amperage  of 
350  or  400,  from  2£  to  3  volts  per  cell  will  be  required.  The  rather  rapid  deprecia- 
tion of  the  generator  is  said  to  have  held  back  its  use  to  some  extent.  Owing  to 
the  lightness  of  the  materials  employed  and  also  possibly  because  of  insufficient 
electrode  surface,  the  anode  is  liable  to  be  attacked  and  eventually  worn  away.  The 
minute  particles  of  iron  or  iron  compounds  formed  are  said  to  have  a  tendency  to 
be  deposited  on  the  cathode.  The  insulators,  employed  to  prevent  the  contact  of 
electrode  with  the  compartment  wall,  form  a  convenient  place  of  deposit  for  the 
iron  particles  with  possible  danger  of  causing  a  short  circuit  between  the  electrode 
and  the  compartment  walls.  If  one  compartment  is  short  circuited  the  entire  cell 
becomes  "shorted"  and  this  short  circuit  will  cause  the  generation  of  mixed  gas. 
The  entire  cell  should  be  dismantled  about  once  a  year  and  cleaned  with  either  a 
stream  of  water  or  by  means  of  a  sand  blast. 

The  American  Oxhydric  Company,  Milwaukee,  Wis.,  have  had  generators  of 
the  Garuti  type  in  operation  for  several  years. 


548 


THE  HYDROGENATION  OF  OILS 


FIG.  108.     Garuti  generator. 


FIG.  109.     Battery  of  Garuti  generators. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          549 


FIG.  110.    One  form  of  the  Garuti  generator. 


FIG.  111.     A  modified  form  of  the  Garuti  generator. 


550 


THE  HYDROGENATION  OF  OILS 


apparatus  is  set  on  insulating  porcelain  feet.  The  normal  type  of 
apparatus  is  built  to  take  750  amperes  at  3  volts  drop  of  potential,  and 
furnishing  eleven  cubic  meters  of  oxygen  and  twenty-two  cubic 
meters  of  hydrogen  per  twenty-four 
hours,  using  up  162  kilowatt-hours.* 
Fiersot  describes  f  an  apparatus  of 
Siemens  and  Halske  for  the  electrol- 
ysis of  water  in  which  a  10  per  cent 


FIG.  112. 


FIG.  113.      Plan  and  elevation  of 
Siemens  Bros,  and  Obach  generator. 


solution  of  potassium  carbonate  is  used  as  electrolyte.  One  hundred 
and  thirty-four  grams  of  water  are  decomposed  per  kilowatt-hour. 
By  heating  the  electrolyte  the  output  may  be  increased  by  8  per  cent. 
The  electrolytic  oxygen  thus  produced  is  on  the  average  97  per  cent 
pure,  while  the  hydrogen  contains  one  per  cent  of  oxygen. 

Another  form  of  metallic   diaphragm   cell   has   been   devised   by 
Fischer,  Luening  and  Collins.|      The  generator  consists  of  a  tank 

*  Jour.  Franklin  Tnst.  (1905),  392. 
t  Electrochemical  Ind.  (1904),  28. 
t  U.  S.  Patent  1,004,249,  Sept.  26,  1911. 


.HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          551 

containing  an  electrolyte  in  which  an  indifferent  number  of  indepen- 
dent, preferably  oblong,  metallic  cases  are  submerged.    An  illustration 
4  of  the  case  is  shown  in  Fig.  114.    The 

A  case  is  open  at  the  bottom  and  is 

Ifl     Jffli^^Hn     divided    into    a   pair   of    cells   by   a 
jy^vSffl!      metallic  diaphragm.     Electrical  con- 
|U^^[|[i  nections  to  the  anode  and   cathode 

&  and  exit  pipes  situated  on  the  upper 

side  of  the  case  are  provided  for  the 
removal  of  the  gases. 

The  apparatus  of  the  Schuckert  sys- 
tem *  is  constructed,  with  the  excep- 
tion of  the  copper  feed  wires  and  the 
insulating  material,  entirely  of  iron. 
The  cell  proper  of  a  unit  designed  to 
accommodate  600  amperes  consists  of 
a  cast-iron  trough  (Fig.  115),  approx- 
imately   twenty-six    inches    long    by 
eighteen  wide  and  fourteen  deep,  re- 
quiring, when  in  operation,  about  50  liters  of  electrolyte.    In  this  trough 
are  placed  the  iron  electrodes.     These  are  separated  by  strips  of  a  good 
insulating  material,  extending  from  the  top  downward  about  three- 


FIG.  115.    Schuckert  cell 

fourths  the  depth  of  the  cell.  .Between  these  separating  plates  and 
enclosing  the  electrodes  are  suspended  iron  bells,  which  collect  and 
carry  off  the  gas  there  generated.  The  electrolyte  is  usually  a  20  per 

*  Electrochem.  Ind.  (1903),  579. 


552 


THE  HYDROGENATION  OF  OILS 


cent  aqueous  solution  of  pure  sodium  hydrate,  although  a  15  per  cent 
solution  may  be  used.  The  concentration  is  maintained  by  supplying 
to  the  cells  an  amount  of  distilled  water  equal  to  that  decomposed  and 
carried  away  mechanically  by  the  gas.  The  loss  of  sodium  hydrate 


FIG.  116.     Longitudinal  section  of  Schuckert  cell. 

is  inappreciable  and  may  be  entirely  eliminated  if  the  first  wash  water 
be  used  as  feed  water  for  the  cells.  The  units  may  be  connected 
either  in  series  or  parallel  with  a  drop  of  potential  between  electrodes 
of  from  two  and  one-half  and  three  volts.  The  apparatus  is  operated 


FIG.  117.      Cross  section  of  Schuckert  cell. 


most  economically  at  a  temperature  of  70°  C.  When  the  cells  are 
protected  from  radiation,  as  can  be  done,  for  example,  by  placing 
them  on  wooden  boxes  and  packing  them  in  one  or  two  inches  of 
sand,  the  heating  effect  of  the  passing. current  is  sufficient.* 

*  The  Elektrizitiits-A-G.  Vorm.  Schuckert  &  Co.  have  taken  out  German 
Patent  231,545,  Aug.  13,  1910,  for  the  addition  of  soaps  or  soap-forming  substance.*, 
preferably  emulsified  soaps,  and  of  ferric  oxide  to  the  alkaline  electrolyte  employed. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER  553 


FIG.  118. 


FIG,  119. 


554 


THE  HYDROGENATION  OF  OILS 


The  standard  types  of  apparatus  are  designed  to  take  from  100  to  1000  amperes, 
and  to  furnish  gas  at  a  pressure  equal  to  a  water  column  of  70  to  80  mm.  For 
special  purposes  a  cell  delivering  gas  sustaining  a  water  column  of  760  mm.  may  be 
secured.  The  production  of  normal  types  of  apparatus  is  about  150  liters  of  hydrogen 
and  75  liters  of  oxygen  per  kilowatt-hour  when  measured  over  water  at  atmospheric 
pressure,  and  at  20°  C.  The  attention  required  for  a  plant  of  this  kind  consists 
simply  in  supplying  the  requisite  amount  of  water  to  maintain  the  concentration 
constant.  When  in  continuous  operation  the  positive  electrode,  which  is  made  up 
of  a  sheet  iron  plate  two  millimeters  thick,  should  be  replaced  at  the  end  of  each 
year.* 

Fig.  118  shows  the  interior  of  a  plant  furnishing  1200  cubic  meters 
hydrogen  daily.  Fig.  119  shows  the  exterior  of  this  plant.  An  equip- 
ment for  an  hourly  production  of  4  cubic  meters  hydrogen  is  shown 
in  Fig.  120.  Fig.  121  is  a  compression  room  for  charging  cylinders 
with  oxygen  at  150  atmospheres  pressure. 


FIG.  120. 


A  modified  form  of  the  Schuckert  cell,  as  shown  in  Figs.  122  and  123,  comprises  a 
container  tank,  constructed  of  welded  sheet  iron  and  a  number  of  positive  and  nega- 
tive electrodes  immersed  in  the  solution.  Eight  separate  bell  castings  are  employed 
to  house  the  electrodes  and  collect  the  gas  as  it  is  generated.  These  bell  castings 
are  made  of  a  close-texture  gray  iron  and  are  suspended  from  the  top  of  the  container 
tank  by  means  of  U-shaped  steel  supports.  The  container  tank  and  the  bell  castings 

*  See  Sci.  Am.  Suppl.  (1913),  363. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


555 


play  no  part  in  the  operation  of  the  generator  and  are  insulated  from  the  electrodes 
and  all  current-carrying  metal.  The  electrodes  are  made  of  steel  plates  to  each  of 
which  are  welded  two  steel  rods,  both  rods  serving  as  terminals  as  well  as  supports 
for  the  electrode,  holding  it  in  position  within  the  bell  casting.  The  electrodes  are 
alternately  positive  and  negative.  All  of  the  positive  electrodes  are  connected 
together  by  means  of  bus  bars  across  the  top  of  the  tank  and  are  led  to  a  common 
terminal.  The  negative  electrodes  likewise  are  connected  together  and  led  to  a 
common  terminal.  Each  bell  casting  is  tapped  for  an  eduction  pipe  to  draw  off 
the  gas  as  generated.  The  four  hydrogen  pipes  are  connected  together  as  shown 
and  are  led  to  the  hydrogen  pipe  line  connecting  a  battery  of  generators.  The 
oxygen  pipes  are  connected  likewise.  The  electrolyte  fills  the  container  and  owing 
to  its  height  above  the  electrodes  the  gas  is  generated  under  an  appreciable  pressure 
amounting  to  approximately  one  pound  per  square  inch. 


FIG.  121. 


The  novelty  that  distinguishes  the  Schuckert  cell  from  the  majority  of  other  gener- 
ators is  the  absence  of  any  diaphragm  in  the  construction.  While  a  diaphragm  is 
actually  not  used,  still  the  sides  of  the  bell  castings  act  in  the  capacity  of  a  diaphragm 
to  prevent  the  mixing  of  the  gases. 

The  working  efficiency  of  the  Schuckert  cell  under  normal  conditions  of  temper- 
ature is  said  to  average  from  4.5  to  5.5  cubic  feet  of  hydrogen  per  kilowatt-hour  of 
electricity  passed  through  it.  Or,  in  other  words,  the  voltage  required  to  force  400 
to  600  amperes  through  each  cell  will  vary  from  2.9  to  3.5  according  to  the  condition 
of  the  plant.  The  Schuckert  generator  was  one  of  the  earliest  placed  on  the  market 
and  at  the  present  time  three  plants  of  this  type  are  reported  in  use  in  the  United 
States.  Too  high  an  amperage  results  in  so  rapid  an  evolution  of  gas  that  there  is 


556 


THE  HYDROGENATION  OF  OILS 


-2-7T 


a  tendency  under  these  conditions 
for  the  gas  in  one  chamber  to  be 
forced  down  and  under  the  wall 
of  the  next  partition  which,  cf 
course,  will  result  in  mixed  gas  or 
the  escape  of  gas  into  the  gen- 
erator room. 

Another  difficulty  said  to  be 
met  with  in  operating  under  high 
amperage  is  the  wearing  away 
of  the  anode,  charging  the  elec- 
trolyte with  small  particles  of 
iron  compounds  which  show  a 
tendency  to  be  attracted  to  the 
cathode  and  gradually  form  a 
deposit.  These  accretions  have 
been  known  to  build  across  the 
space  between  the  electrode  and 
the  bell  castings  causing  short- 
circuiting  and  permitting  the  bell 
castings  to  become  charged,  with 
consequent  evolution  of  gas  on  its 
outer  side  and  the  escape  of  gas 
into  the  generating  room.* 

Details  of  construction  of  an  electrolytic  apparatus  for  the  production  of  hydro- 

*  The  Schuckert  apparatus  is  supplied  by  the  Elektrizitats-A-iG.  Vorm.  Schuckert 
&  Co.,  Nurnberg.  In  a  private  communication  they  state  that  an  electrolyzer 
battery,  capable,  when  running  at  a  temperature  of  50°  to  60°  C.,  of  producing  hourly 
10  cubic  meters  of  hydrogen,  yields  the  gas  of  99.5  per  cent  purity.  For  this  equip- 
ment they  quote: 

Electrolyzer 

Caustic  soda  (containing  a  little  chlorine  and  sulfur)  1450  kilos  .... 

Insulating  material 

2  scrubbers,  driers,  and  safety  devices,  pressure  regulators  and 

gauges 

2  gas-purifying  stoves 

Packing  for  over  seas  and  freight 

Total .  . 


$2350 
410 
100 

250 
500 
240 


$3850 

Other  auxiliaries  are: 

2  gas  holders  (10  and  20  cubic  meters) $2000 

Wooden  staging  and  boxes  to  contain  the  battery  embedded  in 

sand  for  protection  against  loss  of  heat 200 

Compressors 2850 

Water-distilling  apparatus 200 

Miscellaneous 525 

The  temperature  of  the  electrolyzer  room  should  be  maintained  at  least  at  15°  C. 
In  cold  weather  it  must  be  heated. 

An~electrolytic  hydrogen  and  oxygen  generator  of  the  bell-collector  type  is  de- 
scribed by  Benker  (J.  S.  C.  I.,  1914,  256,  and  French  Patent  461,981,  Aug.  29,  1913). 


HYDWKiKN  BY  THE  ELECTROLYSIS  OF  WATER 


557 


558 


THE  HYDROGENATION  OF  OILS 


gen  and  oxygen  are  given  by  Van  Scoyoc  (U.  S.  Patent  813,844,  Feb.  27,  1906), 
in  which  the  operation  is  rendered  continuous  by  the  use  of  automatic  float-valves. 
The  level  of  the  acidulated  water  in  the  electrolyzer  is  maintained  constant  by 
means  of  a  float- valve  in  the  supply  pipe.  The  two  electrodes  are  placed  in  two 
compartments  which  are  open  at  the  bottom.  Each  compartment  is  divided 
into  a  lower  and  an  upper  chamber,  connection  between  the  two  being  made  by 
automatic  float-valves.  When  the  pressure  of  the  gases  generated  in  the  lower 
chambers  becomes  great  enough  to  lower  the  level  of  the  water,  the  valve  is  opened 
and  the  gases  pass  into  the  other  chamber  and  then  into  gas  bags. 

Aigner*  charges  an  alkaline  electrolyte  into  an  iron  vessel  G,  Fig.  125, 
in  which  an  iron  drum  T  rotates,  the  outer  surface  of  the  latter  being 
amalgamated. 

The  upper  part  of  G  is  divided  into  two  compartments  R  and  Rt  by  the  parti- 
tion S,  which  extends  downwards  nearly  to  the  drum  T.  The  oxygen  and  hydro- 
gen are  led  off  through  separate  outlets  in  the 
cover  D.  The  electrolyte  is  introduced  and  with- 
drawn through  the  opening  L.  At  the  anode  A 
hydroxyl  ions  are  depolarized,  with  formation  of 
water  and  gaseous  oxygen,  the  latter  escaping  into 
the  compartment  R,  while  an  equivalent  quantity 
of  sodium  ions  is  depolarized  and  combines  chem- 
ically with  amalgam  on  the  surface  of  the  drum 
adjacent  to  the  anode.  When  this  portion  of  the 
drum  comes  below  the  cathode  K  hydroxyl  ions 
are  depolarized  with  formation  of  sodium  hydrox- 
ide, the  sodium  being  redissolved  from  amalgam, 
while  sodium  ions  are  depolarized  with  formation 
of  sodium  hydroxide  and  gaseous  hydrogen. 

The  electrodes  of  the  Cowper-Coles 
generatorf  consist  of  metallic  sheets  pro- 
vided with  tongues,  which  project  down- 
wards at  an  angle  of  about  45  degrees  with 

the  faces  of  the  sheets.  These  electrodes  are  placed  in  separate 
collecting  boxes  or  chambers,  the  liberated  gases  being  guided  into 
the  latter  by  the  inclined  tongues  of  metal  which  project  within 
openings  in  the  sides  of  the  chambers.  A  battery  df  generators  may 
be  enclosed  in  a  water  jacket  and  provided  with  means  for  keeping 
the  solution  in  each  cell  at  a  common  level. 

Dansette  (French  Patent  391,793,  Sept.  6,  1907)  has  devised  an  arrangement  for 
feeding  water  vapor  into  the  zone  of  an  electric  arc  produced  in  a  gas-tight  electric 
furnace,  by  passing  water  through  the  lower,  vertical,  carbon  tube,  which  constitutes 
one  of  the  electrodes.  The  furnace  communicates  by  means  of  a  valve  with  a  reser- 
voir, into  which  the  hydrogen  and  oxygen  produced  by  dissociation  pass.  The 
oxygen  may  either  be  absorbed  by  a  suitable  reagent,  or  the  two  gases  separated  by 
diffusion  through  a  porous  earthenware  vessel. 

*  German  Patent  198,626,  Nov.  13,  1906. 
f  British  Patent  14,285,  Dec.  20,  1907. 


FIG.  125. 


HYDIKXJEN  BY  THE  ELECTROLYSIS  OF  WATER 


559 


An  elrctrolyzer  for  the  production  of  pure  hydrogen  and  oxygen 
which  is  suggestive  of  the  Schmidt  type  has  been  designed  by  Eycken, 
Leroy  and  Moritz.*  The  electrode  plates  are  built  up  with  separating 
diaphragms  of  asbestos,  in  the  form  of  a  filter-press.  Openings  in  the 
top  of  each  plate  form  two  channels  for  the  escape  of  the  gases.  The 
gases  are  kept  at  a  pressure  above  that  of  the  atmosphere,  rendering 
the  danger  of  accidental  mixing  remote.  The  electrodes  and  dia- 
phragms are  kept  clean  by  making  the  first  electrode  hollow,  and  in 
the  form  of  a  large  reservoir,  in  which  the  sediment  accumulates  and 
from  which  it  may  be  removed  from  time  to  time.  This  reservoir  is 
divided  into  two  parts,  into  which  the  gases  pass,  through  the  electro- 
lyte, the  pressure  being  maintained  constant,  and  the  delivery  of  the 
gases  regulated  by  two  floats  and  balanced  valves. 


FIG.  126. 


Siegfried  Barth  of  Dusseldorf  builds  "  oxhydrogenerators "  constructed  in  accord- 
ance with  the  foregoing  system.  The  parts  of  the  generator  are  very  heavy  so  that 
durability  is  insured.  The  electrode  plates  are  insulated  by  extra  heavy,  almost 
indestructible,  diaphragms.  A  very  powerful  circulation  of  the  electrolyte  over  the 
surface  of  the  electrode  is  obtained,  resulting  in  an  efficient  removal  of  the  gas 
particles  which  otherwise  would  cling  to  the  electrodes  for  a  considerably  longer 
period.  Great  pains  have  been  taken  to  guard  against  mixing  of  the  gases  so  as  to 
procure  pure  products.  Caustic  soda  or  potash  in  distilled  water  is  used  as  the 
electrolyte.  When  used  uninterruptedly,  the  cell  becomes  warm  and  its  output  is 
improved,  and  for  intermittent  operation  a  steam-heating  arrangement  is  attached 
to  the  generator  so  that  it  may  be  heated  quickly  and  brought  to  full  capacity  with- 
out loss  of  time.  The  ordinary  type  of  this  generator  is  made  to  deliver  both  hydro- 
gen and  oxygen  under  a  pressure  of  about  50  to  80  cubic  meters  water  column,  but 
special  forms  are  furnished  which  operate  under  a  pressure  of  about  4  kilos  (8  to 
9  pounds).  A  generator  having  an  output  of  6.6  cubic  meters  of  hydrogen  and  3.3 
cubic  meters  of  oxygen  per  hour,  requiring  160  amperes  at  250  volts  is  4.4  meters 

*  French  Patent  397,319,  Dec.  9,  1908. 


560 


THE  HYDROGENATION  OF  OILS 


long,  0.72  meter  wide,  and  2.05  meters  in  height,  and  weights  6600  kilos;  the  cost 
being  $2175.     (Fig.  126.)* 

Another  apparatus  of  the  filter-press  type  f  is  designed  especially 
to  produce  the  gases  at  relatively  high  pressure  without  the  purity  of 
the  product  being  affected.  Fig.  127  shows  a  form  of  electrode  plate 
and  Fig.  128  a  view  of  one  end  of  the  generator,  showing  a  collecting 
tower  with  regulator  float  and  a  series  of  plate  electrodes.  J§ 

The  electrolytic  cell  of  Tommasini  as  shown  in  Fig.  129  contains 
vertical  anodes  6  and  cathodes  in  the  form  of 
inverted  U-shaped  receptacles  5.      The  outside 
of  these  receptacles  5  is  covered  with  an  insu- 
lating apron  7  which  extends  to  a  point  above 
the  liquid  line,  and  to  a  point  below  the  lower 
edge  of  the  cathode  5  proper,  so  that  an  over- 
hanging apron  8  is  provided.    The  gases  evolved 
at  the  plates  6  and  accumulated  in  the  top  of 
the  inverted  receptacles  5  are  conducted  off  sep- 
arately, the  hydrogen  passing  through  the  pipe 
12  into  the  safety  device  14.      The  height  of 
water  is  less  in  the  safety  device  14  than  in  the 
receptacles  5,  so  that  when  the 
pressure   of    the    hydrogen    gas 
becomes  so  great  as  to  tend  to 
press  the  fluid  out  of  the  cham- 
bers 5   (which   would   result   in 
the  mixing  of  the  hydrogen  with 
oxygen)  the  pressure  of  the  hy- 
drogen gas  will  first  press  the 
water  out  of  the  receptacle  19 


FIG.  127. 


FIG.  128. 


and  pass  out  of  slots  20,  so  as  to  relieve  the  pressure  in  the  receptacles 
5.  The  aprons  8  at  the  bottom  of  the  compartments  5  also  prevent 
mixing  of  the  two  gases.  || 

*  A  multiple-cell  electrolytic  generator  has  been  patented  by  Levin,  U.  S.  Patent 
1,094,728,  April  28,  1914,  assigned  to  the  International  Oxygen  Co. 

t  Moritz,  U.  S.  Patent  981,102,  Jan.  10,  1911. 

t  In  the  generator  of  L'Oxhydrique  Francaise  (French  Patent  459,967,  Sept.  21, 
1912,  and  addition,  June  25,  1913),  the  diaphragm  of  each  element  is  composed  of 
asbestos  fabric,  which  is  nipped  between  two  wooden  frames.  The  latter  are  bored 
so  as  to  provide  conduits  for  the  evolved  gases  and  the  electrolyte.  The  electrodes 
are  composed  of  light  sheet  iron,  grooved  or  corrugated,  so  as  to  possess  as  much 
active  surface  as  possible.  The  electrodes  may  be  nickelled  on  their  anode  sides. 
The  apparatus  comprises  a  series  of  such  elements. 

§  See  also  U.  S.  Patent  Reissue  13,643,  Nov.  11,  1913. 

II  U.  S.  Patent  1,035,060,  Aug.  6,  1912. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


561 


Buffa  (Electrician  (1900),  4G)  states  that  one  of  the  chief  difficulties  met  with  in 
the  electrolysis  of  water  on  the  large  scale  is  the  mixing  of  the  oxygen  and  hydro- 
gen given  off  at  the  two  electrodes.  If,  in  order  to  avoid  this  mixing,  a  diaphragm 
be  introduced,  the  resistance  of  the  cell  increases  to  such  an  extent  that  the  efficiency 
of  the  apparatus  is  seriously  reduced.  A  better  method  is  to  use  metallic  septa; 
these  separate  the  two  gases  perfectly,  and  act  as  intermediate  electrodes.  Since 
the  reduction  of  voltage,  both  from  the  anode  to  one  side  of  the  septum  and  from 
the  other  side  of  the  septum  to  the  cathode,  is  insufficient  to  cause  decomposition 


FIG.  129. 

of  the  water,  liberation  of  the  products  of  electrolysis  does  not  occur  at  either  sur- 
face of  the  metallic  septum,  but  is  confined  to  the  electrodes  proper.  In  practice, 
iron  electrodes  in  a  1 1  per  cent  solution  of  caustic  soda  have  been  found  to  be  most 
convenient  and  economical.  The  electrolyte  is  covered  with  a  film  of  mineral  oil, 
in  order  to  prevent  absorption  of  carbon  dioxide  from  the  air.  It  has  been  observed 
that  the  same  protective  action  is  afforded  by  a  film  of  water  vapor,  which  obtains 
when  the  temperature  of  the  electrode  is  fairly  high;  when,  however,  the  temperature 
drops  to  10°  C.  or  under,  absorption  of  carbon  dioxide  takes  place  rapidly. 

With  the  object  of  completely  preventing  admixture  of  the  two 
gases  and  at  the  same  time  keeping  the  electrical  resistance  low, 
Vareille  arranges  the  electrodes  as  shown  in  Fig.  130.  Vertical  rows 
of  V-shaped  troughs  are  provided  with  suitable  insulation  and  serve 
to  separate  the  positive  and  negative  electrodes  which  are  placed  on 
opposite  sides.  The  extremities  20  of  these  troughs  are  lower  than 
the  ends  of  the  electrodes  13,  so  that  the  bubbles  of  gas  coming  from 
the  latter  cannot  mix.  The  electrodes  are  both  insulated  from  the 
container.* 

In  a  modification,  the  troughs,  described  above,  for  the  separation  of  the  electrodes 
are  replaced  by  vertical  series  of  elements  each  of  triangular  section,  and  either  solid 
or  hollow.  Each  electrode  consists  of  a  sheet,  with  U-shaped  pieces  bound  on  each 
side  with  rivets.  The  gases  are  collected  in  bells,  either  stamped  out  of  sheet  metal 
or  consisting  of  sheets  cut  out  and  folded,  and  united  at  the  angles  by  autogenous 
soldering,  f 

*  French  Patent  355,652,  June  27,  1905,  and  U.  S.  Patent  823,650,  June  19,  1906. 

t  First  addition,  Oct.  28,  1908,  to  French  Patent  355,652. 


562 


THE  HYDROGENATION  OF  OILS 


-Water  is  made  more  conductive,  according  to  McCarty  (U.  S.  Patent  736,868, 
Aug.  18,  1903),  by  the  addition  of  tartrate  of  potassium,  tartrate  of  sodium,  or  any 
of  the  citrates  or  other  equivalents,  and  sulfuric  acid.  The  apparatus  (U.  S.  Patent 
721,068,  Feb.  17,  1903)  consists  of  two  tanks,  connected  by  a  pipe  at  about  half 
their  height.  Each  tank  consists  of  an  electrode,  so  located  that  the  upper  ends 
are  about  in  a  line  with  the  axis  of  the  connecting  pipe,  through  which  the  current 
passes  from  one  tank  to  the  other.  Each  of  the  two  tanks  has  an  outlet  at  the  top 
through  which  the  gases  generated  may  be  led  to  suitable  holders. 


FIG.  130. 


FIG.  131. 


Another  apparatus  (McCarty,  U.  S.  Patent  816,355,  March  27,  1906)  consists 
of  two  receptacles,  each  containing  one  electrode  and  connected  by  a  conduit  near 
the  bottom.  Each  electrode  is  a  plate  of  platinum  coiled  upon  itself  a  number  of 
times  and  has  a  projecting  terminal  portion  directly  opposite  the  end  of  the  conduit. 
In  still  another  type  (McCarty,  814,155,  March  6;  see  also  813,105,  Feb.  20,  1906) 
the  electrolytic  cell  is  divided  into  two  compartments  by  means  of  a  solid  diaphragm, 
which  is  perforated,  short  glass  tubes  being  inserted  in  each  perforation. 

The  Burdett  system  *  of  electrolytic  apparatus  consists  of  a  varying 
number  of  generators  or  units,  connected  electrically  in  series.  The 
unit,  Fig.  131,  comprises  a  container  enclosing  the  electrodes  and  electro- 
lyte, but  the  walls  of  the  container  do  not  function  as  electrodes.  It 
is  usually  mounted  on  concrete  foundations  and  is  insulated  both  from 
the  ground  and  from  the  generator  proper.  The  electrodes  are  ar- 
ranged on  the  multiple  system,  there  being  a  number  of  both  positive 
and  negative  electrodes  in  each  unit.  The  electrodes  are  separated 
from  each  other  by  a  partition  of  specially-prepared  asbestos  cloth 
which  under  the  conditions  of  operation  is  permeable  to  the  solution 
but  not  to  gas. 

*  U.  S.  Patent  to  Burdett,  1,086,804,  Feb.  10,  1914. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER  563 

A  bell  or  box  casting,  open  at  the  bottom,  is  used  for  housing  the 
electrodes  and  the  asbestos  diaphragm  is  stretched  across  the  box 
casting  from  one  side  to  the  other,  forming  a  number  of  compartments. 
In  each  of  the  compartments  an  electrode  is  placed  running  parallel 
to  the  asbestos  curtain  or  diaphragm.  The  electrical  connections  are 
so  arranged  that  commencing  with  and  including  the  first  electrode, 
every  other  electrode  is  a  cathode,  the  alternate  electrodes  being 
anodes.  At  the  top  of  the  container  the  electrode  terminals  are  joined 
by  means  of  copper  bus  bars,  thus  bringing  all  the  anodes  to  a  common 
anode  terminal  and  all  of  the  cathodes  to  a  similar  connection. 

The  gas  generated  at  the  electrodes  rises  and  is  collected  in  the 
separate  gas-tight  compartments.  These  compartments  are  joined 
by  two  cored  gas  passages  in  the  bell  casting  and  the  gases  pass  through 
these  passages  into  and  through  glass  indicators  and  purgers  to  the 
gas  mains.  Inserted  in  each  of  the  service  mains  is  a  gas  meter,  a 
flash-back,  and  a  water  purger  which  removes  the  water  held  in  sus- 
pension in  the  gas  and  at  the  same  time  acts  as  a  pressure  regulator 
for  the  generators.  Purifiers  are  usually  inserted  in  each  line  to 
cleanse  the  gas.  The  hydrogen  and  oxygen  are  led  to  their  respective 
gasometers  and  from  there  are  compressed  into  storage  tanks  for  use. 
By  means  of  controls  the  compression  may  be  taken  care  of  auto- 
matically.* 

The  automatic  control  feature  of  the  Burdett  apparatus  is  useful. 
By  means  of  electrical  regulating  devices  the  entire  electrolytic  equip- 
ment is  under  automatic  control.  It  also  serves  as  a  safety  device, 
preventing  over-generation  of  gas  or  undue  pressure  on  any  parts 
of  the  apparatus.  The  compressor,  when  the  collecting  gasometer 
reaches  a  predetermined  height,  will  automatically  start,  and  will 
stop  when  the  gasometer  falls  to  a  predetermined  level.  Electric 
control  is  provided  which  will  stop  the  motor  of  the  compressor 
when  the  storage  tank  pressure  reaches  a  certain  point,  starting  the 
motor  when  the  pressure  falls  again,  and  another  control  is  provided 
which  will  stop  the  generation  of  gas  when  both  gasometer  and  storage 
tank  are  charged  to  their  full  capacity. 

Fig.  132  shows  a  battery  of  Burdett  generators  and  Fig.  133  illustrates 
a  complete  equipment  embracing  motor-generator,  gasometers,  storage 
tanks  and  automatic  control  devices. 

Each  generator  operating  under  a  current  of  400  amperes  will  produce  in  excess 
of  6  cubic  feet  of  hydrogen  and  one-half  this  amount  of  oxygen  per  hour,  or  in  round 
numbers,  150  cubic  feet  of  hydrogen  and  75  cubic  feet  of  oxygen  per  24-hour  day 

*  The  author  is  indebted  to  Mr.  Paul  Pleiss  for  a  description  of  the  Burdett 
generator,  also  for  some  data  on  the  Garuti  and  Schuckert  cells. 


564 


THE  HYDROGENATION  OF  OILS 


with  the  gas  measured  at  20°  C.  and  760  mm.     It  is  desirable  to  operate  the  plant 
as  continuously  as  possible  and  a  run  of  23  or  24  hours  per  day  is  recommended. 

Each  cell  operating  under  normal  conditions  will  require,  with  a  solution  temper- 
ature of  80°  F.  about  2  volts  for  the  passage  of  400  amperes.  Thus  each  cell  requires 
about  800  watts  (0.8  kilowatt-hour)  per  hour  to  produce  about  6  cubic  feet  of 


FIG.  132. 

hydrogen  per  hour.  The  efficiency  of  the  generator  is  therefore  high.  If  the  cell 
generator  be  artificially  heated  the  consumption  of  electricity  may  be  decreased 
by  about  10  per  cent  with  a  corresponding  increase  in  the  efficiency  of  the  unit. 
The  hydrogen  will  average  in  purity  99  per  cent  or  higher. 


FIG.  133. 

Electrolytic  apparatus  designed  by  Hazard-Flamand  *  is  shown  in 
Fig.  134.  Between  the  inner  and  outer  electrodes  a  porous  diaphragm 
is  inserted  and  a  fluid  seal  is  disposed  about  both  sides  of  the  top  of  the 


Co. 


*  U.  S.  Patent  1,003,456,  Sept.  19,  1911,  assigned  to  the  International  Oxygen 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


565 


diaphragm  and  is  composed  of  an  outer  seal  and  an  inner  seal,  con- 
sisting of  two  concentric  troughs  one  within  the  other.  The  elec- 
trolyte is  fed  into  the  inner  trough,  passes  to  the  outer  trough  and 
is  delivered  from  the  latter  on  both  sides  of  the  diaphragm.* 


FIG.  134. 

The  I.  O.  C.  System  (International  Oxygen  Co.)  is  a  well-standard- 
ized method  of  generating  hydrogen  and  oxygen.  The  electrolytic 
cell  used  is  very  simple,  an  outside  view  being  given  in  Fig.  135  and  a 
diagram  in  Fig.  136.  The  iron  tank  or  container  serves  as  the  cathode, 
being  connected  to  the  negative  pole  of  the  electric  supply  circuit. 
From  the  cover  of  this  tank  is  suspended  a  perforated  tank  which 
serves  as  the  anode,  being  connected  to  the  positive  pole  of  the  supply 
circuit.  It  is  made  of  a  specially  selected  low-carbon  steel,  to  pre- 
vent the  formation  of  spongy  rust.  By  means  of  an  asbestos  sack, 
suspended  from  the  cover  between  anode  and  cathode,  two  separate 
compartments  are  formed.  At  the  top  these  compartments  are 
sealed  by  a  hydraulic  joint.  Through  an  opening  in  the  c^ver  a  solu- 
tion of  caustic  alkali  in  distilled  water  is  poured  into  the  hydraulic 

*  See  also  U.  S.  Patent  646,281,  March  27,  1900,  to  Hazard-Flamand. 


566 


THE  HYDROGENATION  OF  OILS 


FIG.  135. 


SECTIONAL  VIEW 
I.O.C.  GENERATOR  TYPE  20tt 


FIG.  136. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


567 


joint  and  distributed  in  the  two  compartments.     The  whole  cell  is 
placed  on  insulating  supports  of  porcelain. 

The  oxygen  and  hydrogen  gases  evolved  do  not  pass  directly  from 
their  compartments  to  the  off-take  pipes,  but  first  bubble  through 
water  contained  in  the  two  " lanterns"  on  top  of  the  cell.  They  enable 
the  operator  to  see  at  a  glance  how  the  cell  is  working.  The  purity 
of  the  gases  produced  is  very  high.  A  sample  of  hydrogen  produced 


FIG.  137.     Battery  of  I.  O.  C.  generators. 

by  this  electrolyzer,  analyzed  by  the  Conservatoire  National  des  Art 
et  Metier  in  Paris,  showed  99.70  per  cent  hydrogen,  the  fraction  of 
the  impurities  being  so  small  that  they  were  not  examined. 

All  that  is  required  for  the  operation  of  the  cell  is  the  daily  addition 
of  somewhat  over  a  gallon  of  distilled  water  to  make  up  for  the  quan- 
tity decomposed  into  hydrogen  and  oxygen.  The  daily  output  is 
approximately  72  cubic  feet  of  oxygen  and  144  cubic  feet  of  hydrogen. 
As  to  the  electrical  energy  requirements  a  joint  test  *  made  in  Novem- 
ber, 1910,  by  the  Laboratoire  Centrale  de  PElectricite  and  the  Con- 
servatoire National  des  Arts  et  Metier  with  two  unit  cells  of  this  type 
of  electrolytic  cell  showed  that  the  production  of  I  cubic  foot  of  oxy- 
*  Met.  and  Chem.  Eng.  (1911),  471. 


568 


THE  HYDROGENATION  OF  OILS 


gen  and  2  cubic  feet  of  hydrogen  requires  0.2797  kilowatt-hour.  Re- 
versely 1  kilowatt-hour  produces  3.54  cubic  feet  of  oxygen  and  7  cubic 
feet  of  hydrogen.  Each  unit  cell  requires  a  little  above  2  volts  and 
from  300  to  400  amperes.  A  current  of  350  amperes  produces  about 
65  cubic  feet  of  oxygen  and  130  cubic  feet  of  hydrogen  per  day. 


!      I 


FIG.  138. 

The  following  table  gives  the  results  of  a  test  recently  made  by  the  Electrical 
Testing  Laboratories  of  New  York  for  the  International  Oxygen  Co. 


Cell  No. 

Average 
am- 
peres 

Average 
volts 

Average 
watts 

Maximum 
temp. 

Purity  of 
oxygen 

Cubic  feet 
per  hour 

Cubic  feet  per 
kilowatt-hour 

Oxy- 
gen 

Hydro- 
gen 

Oxy- 
gen 

Hydro- 
gen 

8 

405.1 
405.0 
368.8 
392.0 

2.388 
2.562 
2.826 
2.660 

967 
1038 
1042 
1043 

31.8°  C. 
30.0°C. 
32.0°C. 
26.  5°  C. 

97.73% 
98.67% 
98.46% 
98.50% 

3.247 
3.239 

2.886 
3.082 

6.184 

5^788 
6.254 

3.358 

3.120 
2.770 
2.955 

6.395 

5^555 
5.900 

14  

66  

70  

Average 

392.7 

2.609 

1022 

30.1°C. 

98.34% 

3.114 

6.075 

3.051 

5.950 

HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


569 


The  four  cells  tested  were  selected  as  being  representative  of  the  entire  battery 
after  taking  a  set  of  preliminary  electrical  measurements  on  each  of  the  cells. 

All  of  the  data  given  herewith  are  from  readings  as  actually  observed  and  cor- 
rected for  instrument  errors.  Gas  volumes  are  corrected  for  moisture  and  calculated 
to  20°  C.  and  760  mm. 


FIG.  139. 


The  main  item  of  operating  expense  is  the  cost  for  the  electric  current.  In  New 
York  City  the  wholesale  rates  are  higher  than  in  many  other  large  cities  and  vary  from 
5  to  3  cents  per  kilowatt-hour,  according  to  the  size  of  the  plant;  since  1  kilowatt- 
hour  produces  about  3  cubic  feet  of  oxygen  and  6  cubic  feet  of  hydrogen,  the  electric 
power  cost  for  producing  1000  cubic  feet  of  oxygen  and  at  the  same  time  2000  cubic 
feet  of  hydrogen  would  be  between  $16.70  and  $10.00.  However,  in  large  manu- 
facturing plants  which  have  their  own  power  houses  the  cost  of  energy  is  much 
less;  thus  it  is  known  that  at  the  South  Chicago  works  of  the  U.  S.  Steel  Corporation 
the  electrical  energy  supplied  to  the  electric  furnaces  is  charged  at  the  rate  of  half 


570  THE  HYDROGENATION  OF  OILS 

a  cent  per  kilowatt-hour.      At  this  rate  the  electric  power  cost  for  producing  1000 
cubic  feet  of  oxygen  and  2000  cubic  feet  of  hydrogen  would  be  $1.67. 

Besides  the  electric  power  cost  there  is  the  cost  for  distilled  water  and  for  attend- 
ance. The  latter  is  a  small  item,  and  the  cost  for  the  distilled  water  which  must  be 
added  to  the  cells  to  make  up  for  the  water  electrolyzed  may  be  calculated  from 
the  fact  that  a  little  over  6  gallons  of  distilled  water  are  required  to  produce  1000 
cubic  feet  of  hydrogen. 

One  of  the  objections  advanced  against  the  electrolytic  system  is 
the  relatively  large  floor  space  which  it  occupies,  and  to  obtain  an 
apparatus  of  a  durable  yet  compact  character  the  author  has  designed 
a  generator  having  T-shaped  ribs  on  both  anode  and  cathode,  afford- 
ing a  large  generating  surface  without  excessive  bulk.  Fig.  138  shows 
a  form  of  anode  and  Fig.  139  the  assembled  generator.* 

A  description  of  the  Bettendorf,  Iowa,  Plant  is  given  f  as  a  typical  electrolytic 
oxy hydrogen  plant.  Fifty  generating  cells  are  connected  in  series  across  a  110- volt 
direct  current  line,  each  cell  requiring  400  amperes  at  2.2  volts  and  producing 
about  3.5  cu.  ft.  of  oxygen  and  7  cu.  ft.  of  hydrogen  per  kilowatt  hour.  The  output 
per  twenty-four  hour  day  is  4000  cu.  ft.  of  oxygen  and  8000  cu.  ft.  of  hydrogen. 
The  oxygen  is  99.5  per  cent  and  the  hydrogen  99.9  per  cent  pure.  The  gases  are 
stored  in  large  tanks  and  for  shipment  they  are  compressed  at  1800  Ib.  per  square 
inch  into  100  or  200  cu.  ft.  steel  cylinders.  The  current  for  the  cells  is  obtained  by 
means  of  a  motor  generator  set:  440- volt  3-phase,  fiO-cycle  induction  motor  con- 
nected to  a  50-kilowatt  shunt  wound,  commutating  pole  generator.  A  20  horse- 
power boiler  furnishes  distilled  water  for  the  cells. 

An  electrolytic  oxygen  and  hydrogen  plant  put  into  operation  J  by  the  National 
Ox-Hydric  Co.,  of  Chicago,  at  the  works  of  the  Fore  River  Shipbuilding  Corporation, 
Quincy,  Mass.,  is  simple  to  operate,  requiring  the  attention  of  only  one  man  to  a 
shift,  the  plant  being  run  continuously  by  three  men  in  three  eight-hour  shifts. 
The  plant  consists  of  a  75-horse-power  Bessemer  crude-oil  engine,  belt-connected 
to  a  45-kilowatt  direct-current  generator;  one  of  the  National  Ox-Hydric  Co.'s 
electrolyzers,  producing  3500  cu.  ft.  of  oxygen  per  twenty-four  hours  and  twice  that 
amount  of  hydrogen;  suitable  gasometers,  compressors,  motors,  and  switchboards 
for  control.  The  oxygen  and  hydrogen,  after  being  produced  from  the  electrolyzer, 
pass  into  steel  gasometers  of  2000  cu.  ft.  capacity  each.  The  National  electrolyzer 
is  of  the  improved  filter-press  type  and  consists  of  a  number  of  decomposition  cham- 
bers connected  in  series.  These  chambers  are  formed  by  clamping  together  a 
series  of  cast-iron  electrodes  so  recessed  and  grooved  that  each  plate  forms,  with 
its  neighbor,  a  chamber  which  holds  the  electrolyte,  and  in  which  the  generation  of 
the  gases  takes  place.  The  electrodes  are  insulated  one  from  the  other  by  means  of 
rubber-bound  asbestos  diaphragms.  The  electrodes  and  diaphragms  are  arranged 
alternately  and  are  supported  by  the  insulated  frame  of  the  filter  press.  The  required 
number  of  electrodes  and  diaphragms  with  the  corresponding  end  plates  are  then 
pressed  tightly  together  by  means  of  a  heavy  screw  standard,  thus  making  the  whole 
equipment  form  a  hermetically  sealed  tank,  the  diaphragms  serving  both  as  an 
insulation  and  gasket,  and  serve  to  form  the  sides  of  the  cells,  preventing  mixture  of 

*U.  S.  Patent  1,087,937,  Feb.  24,   1914. 

fElec.  Rev.  West.  Elec.,  66,  1170,  1915;   Chem.  Aba.,  1915,  2189. 

J  Met.  Chem,  Eng.,  1916,  288, 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          571 

the  two  gases  generated.  The  fact  that  the  electrodes  are  thus  separated  by  the 
diaphragms  causes  one  side  of  the  plate  to  act  as  the  anode  of  one  chamber  and  the 
other  side  as  the  cathode  of  the  adjacent  chamber.  The  electrodes  are  composed 
of  a  special  alloy,  and  are  heavily  coated  with  nickel,  which  prevents  the  formation 
of  deposits  or  the  oxidation  of  the  electrodes  themselves.  The  electrolyzers  are 
designed  for  any  standard  direct  current  circuit,  or  with  the  use  of  a  motor-generator 
set,  for  any  of  the  standard  alternating  current  circuits,  thus  doing  away  with  the 
inefficient  low  voltage,  high  amperage  equipment  necessary  with  the  individual-cell 
type  installation.  These  electrolyzers  are  stated  to  occupy  about  one-fifth  the 
floor  space  required  by  the  individual  cell  type.  The  electrodes  themselves  are 
made  with  corrugated  surfaces,  increasing  the  active  electrode  surface  and  forming 
a  large  number  of  very  small  vertical  channels  through  which  the  gases  rise  freely 
to  the  upper  part  of  the  plates.  At  the  top  of  each  electrode  and  hermetically 
sealed  together  are  chambers  in  which  the  gases  are  separated  from  the  electrolyte. 
From  these  chambers  the  gases  pass  off  into  ducts  extending  through  each  plate, 
these  ducts  forming  continuous  conduits,  owing  to  the  manner  in  which  the  plates 
are  assembled.  The  electrolyte  is  a  21  per  cent  solution  of  pure  caustic  potash  in 
distilled  water.  After  the  electrolyzers  are  once  filled  with  this  solution,  distillqd 
water  is  added  from  time  to  time  to  take  the  place  of  the  water  decomposed;  the 
potash  lasts  many  months.  The  distilled  water  is  fed  to  the  electrolyzer  by  an 
automatic  device  which  maintains  a  constant  level  of  the  electrolyte  throughout 
the  machine.  Under  normal  load  conditions,  the  voltage  required  per  cell  is  two 
volts  or  less.  Therefore,  to  operate  on  a  110- volt  circuit  an  electrolyzer  containing 
55  cells  is  necessary;  and  on  the  same  basis,  110  cells  are  necessary  for  a  220- volt 
circuit.  The  positive  pole  of  the  direct-current  dynamo  is  connected  with  the  first 
electrode  in  the  series,  and  the  negative  pole  is  connected  to  the  last  electrode  of  the 
series.  The  apparatus  is  provided  with  one  collector  for  hydrogen  and  one  for  oxy- 
gen, whereas,  the  individual-cell  type  system  must  have  a  separate  draw-off,  or 
collector,  for  each  cell  in  use.  Assuming  continuous  operation  and  normal  load 
conditions  as  specified,  the  electrolyzers  yield  4  cu.  ft.  of  oxygen  and  8  cu.  ft.  of 
hydrogen  at  atmospheric  pressure  per  kilowatt  hour  of  power  consumed  when  the 
plant  is  operated  at  a  temperature  of  68°  F. 

The  International  Oxygen  Company  has  developed  a  new  style 
oxygen  and  hydrogen  generator  of  the  filter  press  type  under  the  name 
of  the  I.O.C.  bipolar  generator.*  See  Figs.  139a,  1396  and  139c. 

The  unit  type  of  generator  produces  3.2  cu.  ft.  of  oxygen  and  6.4  cu.  ft.  of  hydrogen 
per  clock  hour  and  4  cu.  ft.  of  oxygen  and  8  cu.  ft.  of  hydrogen  per  kilowatt  hour. 

The  I.O.C.  Bipolar  Generator  consists  of  a  series  of  metallic  plates  (electrodes) 
clamped  together  in  a  heavy  frame,  electrically  insulated  from  one  another  and  sep- 
arated by  diaphragms  of  porous  fabric.  Each  pair  of  these  electrodes  forms  a  closed 
cell,  divided  by  the  diaphragm.  These  cells  are  filled  with  an  alkaline  electrolyte 
(caustic  potash  or  soda).  An  electric  current  admitted  at  one  end  plate  passes  on 
through  the  plates  and  the  solution  to  the  other  end  plate.  In  its  passage,  it  de- 
composes the  water  in  the  solution  into  the  two  gases — oxygen  and  hydrogen  which 
are  released  on  opposite  sides  of  each  plate  and  emerge  upward  into  the  gas  offtakes. 

*  Levin;  U.  S.  Patent  No.  1,094,728;  French  Patent  No.  467,945,  Jan.  31,  1914;  Brit- 
ish Patent  No.  3,654,  Feb.  12,  1914;  Met.  Chem.  Eng.,  1916,  108;  U.  S.  Patent  No.  1,199,- 
472. 


572 


THE  HYDROGENATION  OF  OILS 


The  mingling  of  the  oxygen  and  hydrogen  in  each  cell  or  compartment  is  prevented 
by  the  diaphragm  which,  as  the  gases  are  released  and  withdrawn,  the  solution  is 
automatically  replenished  from  a  supply  tank.  The  operation  is  continuous  so  long 
as  current  and  electrolyte  are  supplied.  In  the  smaller  type  of  generator,  the  elec- 
trodes are  carried  on  two  steel  rods  supported  on  two  heavy  end  pieces  or  pedestals 
of  cast  iron.  In  the  larger  generator,  the  side  rods  are  replaced  by  steel  bars.  The 
construction  is  one  of  extreme  rigidity,  absolutely  proof  against  any  distortion  and 
consequent  disarrangement  of  electrodes,  with  resultant  leakage.  The  electrodes 
are  clamped  together  by  a  heavy  screw  working  in  the  rear  support.  A  ball  thrust 
bearing  is  interposed  between  the  end  of  the  clamping  screw  and  the  rear  end  plate, 
contributing  to  the  tightness  of  the  generator  by  doing  away  with  the  tendency  of 
the  electrodes  to  "  ride  up  "  from  the  side  bars  under  screw  pressure.  The  elec- 


Oxygen 
-  Offtake 


FIG.  139a. 


trodes  are  of  a  special  design,*  the  anode  side  being  heavily  nickeled,  while  the 
cathode  side  is  of  commercially  pure  iron.  The  surfaces  of  the  electrodes  carry  ver- 
tical corrugations  which  are  interrupted  by  a  large  number  of  depressions  to  facilitate 
the  flow  of  electrolyte  into  the  cell  and  the  release  of  the  gases  from  it.  At  top  and 
bottom  of  each  electrode  are  two  openings  communicating  by  a  cored  channel 
with  opposite  sides  of  the  plate.  Those  at  the  bottom  are  for  the  water  intake  and 
those  at  the  top  are  for  the  gas  offtake.  Each  half  of  each  cell  (separated  by  the 
diaphragm)  has  its  own  independent  water  intake  and  gas  outlet,  so  that  there  can 
be  no  possibility  of  the  two  gases  mingling  through  these  channels.  Any  gas  leakage 
which  may  occur  between  the  electrodes  escapes  to  the  open  air  and  not  into  the 
adjacent  cell  or  into  the  gas  offtakes.  The  diaphragms  are  of  especially  prepared 
asbestos  fabric.  All  around  the  edge  of  this  fabric  is  moulded  a  packing  rim  of  pure 
rubber  which  rests  in  a  recessed  groove  on  the  face  of  the  electrode. 

In  a  generator  of  this  kind,  an  essential  of  power  economy  is  that  all  the  current 

*U.  S.  Patent  to  Levin,  No.  1,153,168. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


573 


supplied  the  machine  shall  pass  through  the  electrolyte  and  none  of  it  be  by-passed 
through  the  metal  of  the  machine  or  through  the  water  inlets  and  gas  outlets.  The 
electrodes  are  insulated  from  the  side  bars  of  the  frames  by  porcelain  insulators. 
The  electrodes  are  insulated  from  one  another  by  the  pure  rubber  packing  rim 
surrounding  the  diaphragm,  and  by  nipples  of  pure  rubber  inserted  in  the  water 
intake  and  gas  offtake  shoulders  of  the  electrodes.  These  nipples,  when  the  appa- 
ratus is  closed,  meet  one  another  and  not  only  insulate  the  electrode  shoulders  but 


FIG.  1396. 


also  provide  an  insulating  tube  in  the  interior  of  the  water  intakes  and  gas  offtakes. 
The  gases  rising  from  the  electrodes  and  entering  the  gas  offtakes,  carry  with  them 
a  small  percentage  of  the  electrolyte  which,  if  allowed  to  enter  the  external  piping 
system,  would  "  ground  "  the  apparatus  and  permit  the  escape  of  current.  To 
guard  against  this  contingency,  there  is  provided  in  the  gas  offtake  system  insu- 
lating pipe  sections,  each  consisting  of  two  sections  of  heavy  glass  tube  clamped 
between  iron  flanges  and  so  devised  as  to  intercept  and  drain  off  through  an  insu- 


574 


THE  HYDROGENATION  OF  OILS 


lating  connection  the  moisture  entrained  in  the  gases.  The  gases  go  through  these 
insulators  substantially  dry  and  free  from  electrolyte.  The  nickel  anode  and  iron 
cathode  have  been  found  to  materially  facilitate  the  electrolysis,  and  to  lower  the 
over- voltage.  Incidentally,  these  bi-metallic  electrodes  prevent  the  formation  of 
rust  and  oxides  which  would  shorten  the  life  of  the  apparatus.  The  design  of  the 
generator  is  such  as  to  retain  within  the  apparatus  most  of  the  heat  produced  as  a 
result  of  the  resistance  to  the  flow  of  electricity.  This  keeps  the  electrolyte  and 
the  electrodes  at  a  comparatively  high  temperature,  which  adds  to  the  efficiency  of 
the  electrolytic  process.  On  the  front  of  the  generator  are  two  tanks  with  glass 
water-level  indicators,  which  carry  the  solution.  Pipes  descend  from  these  tanks 


FIG.  139c. 

to  a  water-feed  manifold  which  branches  into  two  pipes  connecting  independently 
to  the  two  water  intakes  to  the  cells  and  also  into  two  risers  leading  to  two  inde- 
pendent gas  domes  above.  Into  these  domes,  the  oxygen  and  hydrogen  are  sepa- 
rately discharged  as  generated,  the  gas  offtakes  opening  through  an  inverted  "  U  " 
below  the  fluid  level.  The  proper  fluid  level  is  automatically  maintained  through- 
out the  system.  The  two  independent  water  intakes  to  either  side  of  each  elec- 
trode prevent  mingling  of  oxygen  and  hydrogen  through  the  water  supply.  The 
two  gas  off-takes  discharge  into  the  two  independent  gas  domes  already  referred  to, 
the  gas  emerging  below  the  fluid  surface  through  an  inverted  "  U."  The  pressure 
on  both  gases,  clear  back  to  the  individual  cells,  is  the  same — this  being  controlled 
by  the  hydrostatic  head  in  the  domes  through  which  the  gases  pass.  The 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          575 

escaping  from  the  gas  offtakes  rise  through  the  fluid  in  the  gas  domes  and  pass  out 
through  discharge  pipes  at  the  top  of  the  domes — thence  downward  to  purgers  on 
either  side.  These  purgers  are  closed  boxes  of  cast  iron  filled  with  water  to  a  certain 
level.  The  gases  escape  below  the  surface  of  the  water,  and  pass  upward  through 
it  into  the  supply  lines  to  the  gas  holders.  The  function  of  these  purgers  is  to  catch 
any  entrained  electrolyte  in  the  gas,  to  cool  the  gas,  and  to  act  as  a  water-check- 
valve  protecting  the  pressure  system  of  the  generator  from  any  undue  pressure  of 
the  gasholders.  A  signal  whistle  is  provided  which  gives  notice  when  the  level  of 
the  solution  in  the  generator  falls  below  the  prescribed  level.  Glass  sight-feed  indi- 
cators on  the  solution  tank  and  gas  domes  show  the  fluid  levels  and  reveal  the  gene- 
ration of  the  gases.  Gauge  glasses  connecting  with  the  electrodes  at  intervals  along 
the  generator  show  the  fluid  levels  in  the  body  of  the  apparatus. 

Shriver  *  recommends  an  apparatus  composed  of  several  flat  plates, 
forming  the  electrodes,  bound  face  to  face  to  form  a  cell  of  the  filter- 
press  type,  each  of  the  plates  being  recessed  centrally  to  form  a  cell 
between  the  faces.  A  diaphragm  is  arranged  between  each  pair 
of  plates  to  separate  the  gases  formed  on.  the  faces  of  adjacent  plates, 
the  gases  being  led  from  the  recessed  portions  to  closed  gas  chambers 
above,  through  ducts  in  walls  separating  the  chambers  and  recesses. 
The  gases  are  conveyed  from  the  gas  chambers  to  horizontal  ducts 
extending  through  non-recessed  parts  of  the  plates  from  face  to  face, 
so  that  the  recessed  portions  may  be  completely  filled  with  liquid  to  a 
level  normally  higher  than  the  horizontal  ducts,  without  fear  of  the 
electrolyte  entering  the  gas  ducts,  f 

An  illustrated  description  of  the  Oerlikon  (Schmidt)  electrolyzer  for 
the  commercial  production  of  oxygen  and  hydrogen  is  given  in  Elec- 
trochem.  Z.,  22,  27-42,  1915;  Chem.  Abs.,  1915,  2190. 

An  electrolytic  apparatus,  of  the  filter-press  type,  designed  by  Dohmen,t  ia 
composed  of  a  series  of  cells,  each  comprising  a  thin  quadrilateral  wrought-iron 
frame  having  a  single  central  opening,  and  with  two  passages  through  the  top  of 
the  frame.  A  detachable  sheet  metal  electrode  is  secured  in  the  opening  of  the 
frame,  and  the  top  of  the  latter  is  also  provided  with  two  gas-separating  chambers 
one  at  each  end.  The  chambers  extend  laterally  in  a  downward  direction  to  the 
active  faces  of  the  electrodes  for  conducting  the  gases  from  opposite  sides  to  the  two 
passages. 

A  hydrogen  generator  of  the  unit  or  sectional  type  placed  on  the 
market  by  the  International  Oxygen  Company  offers  advantages  as 
regards  compactness,  high  efficiency,  low  cost  and  flexibility.  Fig.  139d 
shows  a  single  section  or  unit  and  Fig.  139e  indicates  the  method  of 
assembling  the  sections. 

Although  of  the  single  unit  type,  the  cell  is  but  3?  in.  thick  and  in 

*  U.  S.  Patent  No.  1,181,549;  J.  S.  C.  I.,  1916,  1023. 

t  See  also  U.  S.  Patent  No.  1,239,530,  Sept.  11,  1917;  J.  S.  C.  I.,  1917,  1138. 

t  U.  S.  Patent  No.  1,211,687,  Jan.  9,  1917;  J.  S.  C.  I.,  1917,  295. 


576 


THE  HYDROGENATION  OF  OILS 


consequence  100  cells  can  be  stacked  in  a  lengthwise  space  of  less  than 
30  ft.  The  cells  are  approximately  3  ft.  6  in.  wide  and  as  installed  are 
not  in  excess  of  6  ft.  high.  They  occupy  less  space  than  the  filter  press 
type.  These  unit  cells  when  operating  at  their  normal  current  of  600 


FIG.  139d 


amperes  will  produce  4.8  cu.  ft.  of  oxygen  and  9.6  cu.  ft.  of  hydrogen 
per  clock  hour.  They  require  2.22  volts  per  cell  which  establishes  a 
KWH.  efficiency  of  3.65  cu.  ft.  of  oxygen.  When  operated  at  a  current 
less  than  600  amperes  the  electrical  efficiency  is  considerably  increased 
but  the  capacity  is  decreased  and  when  operated  in  excess  of  600  am- 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


577 


peres  there  is  an  increase  in  capacity  but  a  slight  falling  off  in  electrical 
efficiency;   600  amperes  has,  therefore,  been  adopted  as  a  compromise 
between  initial  cost  of  installation  and  operating  cost. 
As  indicating  the  flexibility  of  this  equipment  there  is  tabulated 


below,  the  approximate  performance  at  currents  up  to  as  high  as  1000 
amperes. 


Current. 

Volts  per  Cell. 

Cu.ft.  Oxygen 
per  Hour. 

Cu.ft.  Hydrogen 
per  Hour. 

Cu.ft.  Oxygen 
per  KWH. 

Cu.ft.  Hydrogen 
per  KWH. 

300 

1.94 

2.4 

4.8 

4.17 

8.34 

400 

2.04 

3.2 

6.4 

3.97 

7.94 

500 

2.13 

4.0 

8.0 

3.80 

7.60 

600 

2.22 

4.8 

9.6 

3.65 

7.30 

800 

2.38 

6.4 

12.8 

3.40 

6.80 

1000 

2.54 

8.0 

16.0 

3.16 

6  32 

An  electrolytic  hydrogen  and  oxygen  generator  with  cobalt  as  the 
active  anode  element  and  iron  as  the  cathode  has  been  developed  by 
Levin.* 

*Met.  Chem.  Eng.,  1917,  401;  U.  S.  Patent  No.  1,214,934,  Feb.  6,  1917;  British 
Patent  No.  102,933  and  No.  108,477,  application  date  Oct.  27,  1916. 


578  THE  HYDROGENATION  OF  OILS 

The  generator  unit  consists  of  a  rectangular  thin  iron  plate  casing  of  small 
height,  long  and  narrow.  Any  number  of  these  may  be  joined  together  to  form  a 
complete  generator.  The  iron  casing  is  divided  into  two  parts  by  an  asbestos  dia- 
phragm, suspended  from  an  impermeable  partition  which  reaches  about  one-fourth 
of  the  way  down  into  the  cell  from  the  top.  An  electrode  is  placed  in  each  com- 
partment formed  by  the  diaphragm.  The  partition  in  the  upper  part  of  the  cell 
prevents  the  combination  of  oxygen  and  hydrogen  after  these  gases  have  been 
generated  and  have  risen  separately  to  the  top  of  the  cell,  being  prevented  from  mix- 
ing by  the  diaphragm.  Suitable  means  are  provided  for  carrying  away  the  gases, 
filling  the  generators  with  electrolyte,  etc.  The  anode  is  made  of  iron,  electroplated 
with  a  thin  film  of  cobalt,  and  the  cathode  is  of  iron,  preferably  electrolytic.  The 
electrodes  are  given  a  previous  treatment  by  making  them  the  anode  in  a  solution  of 
a  salt  of  the  active  surface  metal,  and  electrolyzing  for  a  brief  period.  This  is  claimed 
to  give  greater  efficiency  in  operation. 

An  electrolytic  gas  generator  devised  by  Levin  *  is  provided  with  electrodes 
entirely  independent  of  the  container  or  casing.  The  casing  is  divided  into  three 
compartments,  in  each  of  which  an  electrode  is  located.  The  cell  is  of  the  sectional 
type  so  that  a  number  of  units  may  be  assembled  in  a  compact  manner.  The  elec- 
trode compartment  of  the  generator  has  a  gas  outlet  which  is  sealed  with  water, 
and  through  which  water  is  supplied  to  the  compartment,  from  a  chamber  above. 
The  water  chamber  is  provided  with  a  gas  outlet  and  a  water-supply  conduit,  f 

A  form  of  Levin  generator,  made  by  the  Electrolytic  Oxy-Hydrogen 
Laboratories,  Inc.  (Electrolabs)  {  is  compact  and  simple  in  construction, 
being  built  of  a  few  standardized  parts  which  can  be  rapidly  and  ac- 
curately assembled.  The  generator  consists  of  three  compartments. 
The  oxygen  is  generated  in  the  two  outer  compartments  and  the  hydro- 
gen in  the  center  compartment.  Two  sheet-metal  frames,  to  each  of 
which  is  attached  an  asbestos  diaphragm,  serve  as  the  separating 
mediums.  The  electrodes  are  independent  of  the  casing.  They  are 
separated  from  and  securely  fixed  within  the  casing  by  specially 
designed  blocks  of  asbestos.  The  surfaces  of  both  the  anode  and 
cathode  are  plated.  The  use  of  cobalt  for  such  purpose  is  one  of  the 
features  of  this  generator.  Each  compartment  has  an  independent 
water  feed  which  also  serves  the  purpose  of  a  blow-off  device  to  vent 
the  gas  from  each  compartment  under  abnormal  conditions.  A  spe- 
cially designed  sight-feed  indicator  is  placed  between  the  generator 
and  the  gas  offtake  pipe.  Each  indicator  makes  the  generating  unit 
to  which  it  is  attached  independent  of  all  the  other  generators  in  the 
group.  It  further  serves  to  keep  uniform  the  pressure  of  the  oxygen 
and  hydrogen  inside  the  individual  generator.  It  also  enables  one  to 

*  U.  S.  Patent  No.  1,219,966,  Mar.  20,  1917. 

tSee  alsoU.  S.  Patent  No.  1,247  694,  Nov.  27,  1917;  and  1,199,472,  Sept.  26,  1916, 
to  Levin;  Chem.  Abs.,  1918,253;  Canadian  Patent  No.  175,807,  Mar.  20,  1917;  Chem. 
Abs.,  1917,  3001. 

J  15  William  Street,  New  York  City. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          579 


FIG.  139/. 


Anode  Compartment. 


Asbestos  Diaphram. 
FIQ.  1390. 


Cathode  Compartment. 


580 


THE  HYDROGENATION  OF  OILS 


see  at  a  glance  whether  the  gases  are  being  generated  properly.    The 

generator  is  delivered  entirely  welded  and 

i  completely   and   rigidly   assembled.     The 

dimensions  of  the  unit  are  30X25X6J  in. 
The  construction  is  shown  by  Figs.  139/ 
and  1390.  Fig.  139/i  shows  the  assembled 
unit  and  Fig.  139i  is  a  group  of  generators. 
In  a  day  of  twenty-four  hours  this  form 
of  Levin  generator  at  200  amperes  will 
produce  38.4  cu.  ft.  of  oxygen  and  76.8 
cu.  ft.  of  hydrogen,  measured  at  20°  C.  and 
760  mm.  pressure.  A  battery  of  100  gen- 
erators will  occupy  a  space  31  ft.  long  by 
4  ft.  6  in.  wide  and  will  produce. 

In  1  hour 

160  cu.  ft.  oxygen 
320  cu.  ft.  hydrogen 

In  24  hours. 

3840  cu.  ft  oxygen 
7680  cu.  ft.  hydrogen 


FIG.  139ft. 


Each  generator  running  at  200  amperes 
requires  slightly  over  t¥  kilowatt  per  hour. 


FIG.  139i.— Electrolabs  (Levin)  Generators. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


581 


In  a  space  31  ft.  X  4  ft.  6  in.  and  with  a  normal  room  height  (10  to 
12  ft.)  200  Levin  generators  can  be  installed  in  two  tiers. 

Griffin's  apparatus  for  generating  hydrogen  and  oxygen  by  electroly- 
sis *  consists  of  a  cell  and  a  plate  of  conducting  material  depending  into 
water  of  each  cell.  This  plate  is  bent  just  above  the  cell  and  is  attached 
to  the  adjoining  cell,  thus  making  a  continuous  flow  of  current  from 
one  cell  to  the  next.  The  plate  is  enclosed  in  a  sack  of  asbestos  to 
separate  the  oxygen  and  hydrogen.  The  asbestos  sack  may  be  spaced 
from  the  plate  by  some  insulating  material  to  insure  a  complete  separa- 
tion of  the  gases.  (See  Fig.  139y.) 

Kato  states  that  in  the  electrolytic  preparation  of  hydrogen  and 
oxygen,  f  the  diaphragms  used  in  the  commercial  apparatus  do  not  keep 


FIG.  139/. 


FIG.  139&. 


these  gases  completely  separate,  as  shown  by  diffusion  data  given.  Kato 
finds  that  pure  gases  can  be  technically  prepared  without  the  use  of  a 
diaphragm.  Special  electrodes  are  employed  which  have  an  inclined 
active  surface  to  which  the  generated  gas  adheres  by  reason  of  its 
buoyancy  and  accordingly  does  not  diffuse  into  the  solution. 

Halter  has  devised  an  electrolytic  cell  J  (see  Fig.  139&)  for  the  produc- 
tion of  oxygen  and  hydrogen  in  which  a  tank,  acting  as  the  cathode,  is 
provided  with  a  cover,  from  which  the  anode  constructed  of  wires 
united  in  the  form  of  a  hollow  body,  is  suspended  in  the  electrolyte. 

A  separator,  of  porcelain  or  other  non-conducting  and  oxygen-resisting  material, 
is  supported  over  the  anode  with  its  sides  extending  below  the  surface  of  the  elec- 
trolyte, and  the  closed  top  is  provided  with  an  oxygen  outlet.  An  asbestos  sack 
is  secured  to  and  suspended  from  the  separator,  enclosing  the  anode  below  the  sur- 

*U.  S.  Patent  No.  1,117,185,  Nov.  17,  1914. 

t  J.  Chem.  Ind.  Japan,  18,  919,  1915;   Chem.  Abs.,  1916,  561. 

J  U.  S.  Patent  No.  1,172,885  and  1,172,887;  J.  S.  C.  I.,  1916,  476. 


582 


THE  HYDROGENATION  OF  OILS 


face  of  the  liquid,  the  separator  and  sack  constituting  a  complete  non-conducting 
enclosure  for  the  anode.  Means  are  provided  for  conducting  off  the  hydrogen  from 
the  space  beneath  the  cover  of  the  separator.  The  tank  is  made  in  the  form  of  a 
narrow  upright  chamber,  with  a  partition  dividing  the  interior  of  the  tank  into  nar- 
row vertically  arranged  compartments,  the  partition  and  walls  of  the  tank  forming 
the  cathode.  Each  anode  is  formed  from  spaced  perforated  sheet-metal  plates, 
arranged  so  as  to  have  a  hollow  oblong  form  in  horizontal  section,  with  curved 


FIG.  139Z. 


FIG.  139m. 


ends  and  bottom,  and  secured  at  its  upper  edges  to  a  horizontal  conducting  bar 
supported  from  the  cover  of  the  tank.  A  separator  of  non-conducting  material, 
with  attached  sack  enclosing  the  anode,  is  inverted  over  each  anode  and  disposed 
lengthwise  in  the  chamber.  The  partition  is  formed  from  two  plates,  back  to  back, 
with  their  end  portions  curved  apart  and  around  the  ends  of  the  anodes. 

The  Davis-Bournonville  Company  *  system  of  hydrogen  and  oxygen 


generation  embraces   an  electrolyzer   of  a  compact  type, 

*  Jersey  City,  N.  J. 


shown    in 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


583 


Fig.  139/.  The  electrodes  of  this  apparatus  are  of  sheet  metal,  the 
anodes  being  nickeled.*  An  alkaline  electrolyte  is  used.  The  elec- 
trolyzers  are  made  in  two  sizes,  500  and  1000  amperes,  with  a  hydro- 


FIG.  139n. — Swartley  Separator. 

gen  output  of  7.92  and  15.84  cu.  ft.,  respectively.  The  apparatus  is 
assembled  by  the  makers  and  is  shipped  ready  for  immediate  use. 
Fig.  139m  shows  an  anode  of  a  1000  ampere  electrolyzer.  A  Swartlejr 


FIG.  139o. 

hard-rubber  separator  f  (Fig.  139n)  is  shown  at  the  base  of  the  anode. 
The  separator  is  an  inverted  trough-shaped  structure  which  is  disposed 

*  Swartley,  U.  S.  Patent  No.  1,263,959,  April  23,  1918. 
fU.  &.  Patent  No.  1,176,105,  Mar.  21,  I'.Mfi. 


584 


THE  HYDROGENATION  OF  OILS 


over  each  anode  member  and  extends  a  short  distance  below  the  surface 
of  the  electrolyte.  The  separator  supports  an  asbestos  sack  which  covers 
the  anode  member  and  serves  to  confine  the  oxygen.  The  container 
and  partition,  Fig.  139o;  constitute  the  cathode  element.  Fig.  139p 


FIG.  139p. — Assembling  the  Anode  Parts, 

shows  the  method  of  assembling  of  anodes  on  the  cast-iron  electrolyzer 
cover,  one  anode  being  enclosed  in  an  asbestos  sack.  Fig.  139g  shows 
a  typical  arrangement  of  fifty  of  the  500  ampere  electrolyzers.  * 

*  This  type  of  apparatus  is  made  under  the  Bucknam  Patent  No.  1,172,932,  Feb.  22, 
1916.  A  description  of  the  Davis-Bournonville  equipment  is  found  in  Oxy-Acetylene 
Welding  by  Miller,  New  York,  1916,  30. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


585 


FIG.  139?. 

SYSTEM  OF  AUTOMATIC  CONTROL 

The  control  of  the  electric  current  employed  in  electrolysis  of  water 
to  produce  oxygen  and  hydrogen  is  of  importance.  Precautions  must 
be  taken  against  the  discharge  of  current  in  a  reverse  direction  from  the 
electrolyzers  through  the  generator.  This  condition,  if  allowed  to 
develop,  may  result  in  reversal  of  the  source  of  energy  and  consequent 
reverse  functioning  of  the  electrolyzers  with  the  attendant  mixing  of 
gases.  There  is  also  to  be  observed  the  prevention  of  improper  con- 
nection of  terminals  at  the  bank  of  electrolyzers  during  or  after  over- 
hauling or  for  other  reasons.  The  Davis-Bournonville  Company  has 
developed  an  electrolyzer  control  which  is  designed  to  prevent  reversal 
of  current  direction  through  cutting  off  the  source  of  supply  auto- 
matically. 

Fig.  139r  shows,  in  a  general  manner,  the  electrical  connections  and  methods  of 
control.  Fig.  139s  shows  the  equipment  assembled  on  a  panel.  The  necessary  indi- 
cating volt  and  ammeters  C  and  D,  respectively,  are  mounted  on  each  panel  of  this 
design;  also,  the  necessary  instruments  for  the  automatic  control  of  the  electrolyzing 


586 


THE  HYDROGENATION  OF  OILS 


circuit.     The  generator  A  is  the  source  of  electrical  energy  for  the  electrolyzers  and 
its  field  regulator  B  is  also  mounted  upon  this  panel.* 

The  electrolyzer  current  proper,  H,  is  controlled  solely  through  the  magnetic 
contactor  F,  the  magnetic  coil  of  which  is  wound  for  operation  across  the  inde- 
pendent supply  mains  G.  This  independent  supply  main  can  be  either  alternating 


Ground 


Field  Regulator 

Contactor 
n    Switch'J" 

Vfi 


Direct  Current  or 
E 'lee  irolyzing  Circuit 


Independent  Circuit    from  Power  House--' 
or  elsewhere  either  A.  C.or  D.C.  "0  " 


FIG.  139r. 


or  direct  current  of  any  voltage.     This  independent  circuit  G  is  controlled  at  three 
separate  and  distinct  points,  as  follows: 

1st— Potential  Relay  E, 

2d — Contactor  Pilot  Switch,  hand  reset,  J, 

3d— Overload  Relay,  hand  reset  M. 

The  potential  relay  E  is  set  to  lift  at  a  predetermined  operating  or  charging  voltage, 
thereby  completing  the  electric  circuit,  which  will  throw  into  play  the  magnetic 
contactor  F.  This  means  that  with  the  contactor  pilot  switch  J,  held  closed  and 
the  overload  relay  closed,  not  until  the  generator  will  have  reached  the  predeter- 
mined charging  voltage  will  the  potential  relay  close  the  independent  circuit  from 
the  power  lines.  It  will  be  noted  that  it  is  impossible  to  pass  electrical  energy 
through  the  electrolyzers  until  the  generator  attains  the  charging  voltage. 

If,  for  any  reason,  during  operation  the  generator  voltage  should  drop  below  the 
charging  voltage,  the  potential  relay  E  will  automatically  drop  out,  opening  the 
magnetic  contactor,  thereby  breaking  the  electrolyzing  circuit.  This  method  of 
control  entirely  prevents  the  electrolyzers  from  discharging  to  the  generator  A,  with 
the  consequent  possibility  of  polarity  changes,  if,  through  error  or  deliberately  revers- 
ing electrical  connections,  the  direction  of  flow  of  electrical  current  is  changed.  The 
smallest  fraction  of  a  reversed  current  through  the  shunt  N  brings  the  polarized 
relay  into  play,  breaking  the  contact  in  the  contactor  switch  J  which,  in  turn, 
breaks  the  current  through  the  coil  of  the  potential  relay  E,  thereby  releasing  the 
connection  O  and  breaking  the  circuit  G,  which  drops  out  the  magnetic  contactor 

*  U.  S.  Patent  No.  1,201,526,  Oct.  17,  1916,  to  Swartley  and  Larsen. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER 


587 


F  which  interrupts  the  main  electric  circuit  to  the  elect  rolyzers.     This  makes  it 
absolutely  impossible  to  operate  on  a  reverse  polarity. 

The  overload  relay  is  manually  operated  and  is  calibrated  slightly  in  excess  of 
the  normal  operating  amperage.     In  case  of  opening  of  the  circuit,  due  to  overload, 


FIG.  139s. 

it  will  be  noted  that  the  overload  relay  M  will  have  to  be  reset  by  hand  before 
the  electrolyzing  circuit  can  again  be  established. 

Under  normal  operating  conditions  the  ground  detector  lights  Q  will  glow  slightly 
but  in  case  of  a  ground  on  one  or  both  legs  of  the  electrolyzing  circuit,  either  or  both 
of  the  lamps  will  glow  brilliantly,  showing  the  ground  to  exist. 


588 


THE  HYDROGENATION  OF  OILS 


Jones  *  has  designed  an  electrolytic  cell  for  the  production  of  hydro- 
gen and  oxygen.  The  apparatus  is  provided  with  a  number  of  elec- 
trodes, and  a  diaphragm  between  adjoining  electrodes  forms  chambers 
for  the  separation  of  the  evolved  gases,  with  gas  ducts  leading  from  them 
and  separate  conduits  connected  with  the  gas  ducts.  The  electrolyte 
is  conveyed  to  the  several  chambers  by  supply  ducts  connected  to  a 
supply  conduit,  the  various  conduits  being  located  beyond  the  elec- 
trodes, and  so  arranged  as  to  be  outside  the  path  of  the  electric  current 
through  the  apparatus.  A  simple  form  of  electrolytic  cell  for  the  pro- 
duction of  oxygen  and  hydrogen  is  proposed  by  Shaw,  f  The  positive 
electrode  is  readily  removable  without  disturbing  the  other  parts. 
Hepburn  {  has  designed  a  bipolar  electrode  generator.  § 

Jaubert  ||  recommends  a  type  of  electrolytic  hydrogen  generator  having  elec- 
trodes covered  by  bells  brought  near  to  each  other  to  diminish  the  resistance.  The 
active  surface  of  each  electrode  projecting  below  the  lower  level  of  the  bell  is  inversely 
proportional  to  the  volume  of  gas  liberated  at  each  electrode,  while  the  volume  of 
each  bell  is  directly  proportional  to  the  volume  of  gas 
liberated.  The  bells  are  provided  with  cocks,  or  outlet 
collectors  for  the  gases,  and  with  insulated  sleeves  for  the 
cables  connected  to  the  electrodes. 

Mueller    and    Rowlands  If    describe    a   water 
electrolyzing  apparatus  made  as  follows: 

A  tank  (Fig.  1390  is  made  in  two  sections,  a  lower 
and  an  upper  section,  electrically  separated  by  an  insulat- 
ing joint  formed  by  a  trough  extending  around  the  top 
of  the  lower  section  and  containing  a  U-shaped  insulating 
gasket  of  soft  rubber  which  forms  a  cushion  and  also  a 
hermetic  seal.  A  liquefiable  insulator  such  as  paraffin 
filling  the  upper  portion  of  the  trough  further  insures  a 
tight  joint  between  the  sections.  The  lower  edge  of  the 
upper  section  rests  in  the  groove  of  the  gasket.  The  in- 
terior of  the  lower  section  is  divided  by  longitudinal  webs 
parallel  with  the  side  walls,  into  equal-sized  cellular  spaces 
which  are  open  at  top  and  bottom,  these  webs  extending 
only  from  the  upper  edge  of  the  section  to  the  top  of  the 
enlarged  base.  The  webs  are  perforated  at  intervals  with 
holes.  The  anodes  (three  in  number)  are  disposed  in  the  spaces  between  the  webs 
and  side  walls  of  the  section  thus  exposing  a  double  surface  to  tl:c  electric  current 

*  U.  S.  Patent  No.  1,212,229,  Jan.  16,  1917;  J.  S.  C.  I.,  1916,  391. 

fU.  S.  Patent  No.  1,208,722,  Dec.  12,  1916. 

J  British  Patent  No.  12,730,  1915;  U.  S.  Patent  No.  1,213,871,  Jan.  30,  1917;  J.  S.  C.  I., 
1916,  1120. 

§  A  description  of  the  Frazer  Generator  is  found  in  U.  S.  Patent  No.  1,262,034,  April 
9,  1918. 

||  British  Patent  No.  102,974,  Dec.  28,  1916;  J.  S.  C.  I.,  1917,  602.  See  also  U.  S. 
Patent  No.  1,255,096,  Jan.  29,  1918. 

If  U.  S.  Patent  No.  1,220,262,  Mar.  27,  1917. 


FIG.  139*. 


HYDROGEN  BY  THE  ELECTROLYSIS  OF  WATER          589 

for  each  anode,  and  hang  in  diaphragms  of  woven  asbestos.  The  lower  section  is 
the  negative  electrode,  while  the  upper  section  is  insulated  from  both  electrodes  and 
is  designated  the  neutral  section.  The  anodes  are  suspended  from  the  cover  which  in 
turn  rests  upon  the  neutral  section  but  is  insulated  therefrom  by  means  of  a  grid- 
shaped  rubber  gasket.  To  insure  gas-tight  joints  between  the  hydrogen  and  oxygen 
chamber,  and  for  sealing  both  chambers  from  the  outer  air,  the  neutral  section  is 
provided  with  a  series  of  parallel  inner  troughs  for  the  former,  and  for  the  latter  is 
provided  with  an  encompassing  outer  trough  in  which  the  depending  marginal  flange 
of  the  cover  is  sealed  by  paraffine  wax  or  pitch.  The  diaphragms  each  consist  of 
two  parts,  the  diaphragm  proper  and  a  hanger.  The  hanger  is  made  of  thin  sheet 
metal,  and  obviates  the  necessity  of  rendering  gas-impermeable  that  portion  of  the 
diaphragm  which  extends  above  the  liquid  level.  It  is  tubular  in  form,  of  the  same 
cross-section  as  the  diaphragm  and  of  sufficient  length  to  extend  below  the  liquid  level. 
It  is  formed  at  its  upper  end  with  an  outwardly  and  downwardly  projecting  flange  of 
proper  form  to  fit  into  the  sealing  trough  which  extends  continuously  around  each 
hanger.  The  cell  represents  a  highly  elaborated  form  of  water  electrolyzing  apparatus 
the  complete  details  of  which  cannot  be  presented  here.  Another  form  of  apparatus 
designed  by  Mueller  and  Rowlands  *  consists  of  a  deep  metal  tank  divided  into 
communicating  compartments  by  vertical  partitions  which  form,  with  the  sides,  a 
series  of  electrodes  of  the  same  polarity.  The  tank  has  an  arched  metal  cover 
from  which  .depend  a  number  of  metal  plates,  one  nearly  to  the  bottom  of  each 
compartment,  forming  a  corresponding  series  of  electrodes  of  opposite  polarity. 
The  cover  is  insulated  from  the  tank  by  a  diaphragm  through  openings  in  which 
the  metal  plates  extend;  and  each  plate  is  surrounded  by  a  tube  of  flexible,  non- 
corrodible  mater ial.f 

According  to  Sebille,t  hydrogen  and  oxygen  are  generated  electrolytically,  then 
cooled  as  they  pass  from  the  generator  into  separate  containers,  the  condensed 
moisture  being  led  back  into  the  generator.  A  diaphragm  is  so  arranged,  containing 
chambers  through  which  the  gases  pass  on  their  way  to  their  respective  containers, 
that  a  predetermined  difference  of  pressure  on  one  side  of  the  system  causes  the 
diaphragm  to  close  the  gas  entrance  to  the  opposite  container,  until  a  balancing 
pressure  has  again  been  raised  on  that  side.  By  means  of  a  body  of  water  the 
gases  are  automatically  compressed  to  a  pressure  higher  than  that  originally  gen- 
erated. Sebille  §  also  describes  a  system  of  gas  storage  chambers  having  automat- 
ically-controlled valves  regulating  the  flow  of  gases. 

A  method  for  the  electrolysis  of  water  to  produce  hydrogen  forms  the  basis  of 
Japanese  Patent  30,437  of  Dec.  4,  1916,  by  the  Yokohama  Fish  Oil  Co.  ||  The  appa- 
ratus is  provided  with  means  for  collecting  hydrogen  and  oxygen  completely  sep- 
arated from  each  other. 

In  a  form  of  electrolytic  cell  for  obtaining  hydrogen  and  oxygen,  described  by 
Churchill  &  Co.,  and  Geeraerd,  <[  a  vertical  series  of  inclined  non-conducting  vanes 
are  arranged  close  to  the  electrodes  to  confine  gas  flow  to  the  space  between  the 
vanes  and  the  electrodes. 

*  U.  S.  Patent  No.  1,219,843,  Mar.  30,  1917. 
t  See  also  U.  S.  Patent  No.  1,221,206,  Apr.  3,  1917. 
t  U.  S.  Patent  No.  1,230,803,  June  19,  1917. 

§U.  S.  Patent  No.  1,222,809,  Apr.  17,  1917;    also  describes  a  system  of  gas  storage 
chambers  having  automatically  controlled  valves  regulating  the  flow  of  gases. 
||  Chem.  Abs.,  1917,  1932. 
If  British  Patent  No.  101,598,  May  11,  1916;  Chem.  Abs.,  1917,  122. 


CHAPTER  XXVII 

PRECAUTIONS  IN  HANDLING  HYDROGEN.     SAFETY 
DEVICES.    PURIFICATION   OF  GAS 

The  handling  of  electrolytically-derived  gases  brings  with  it  the 
possibility  of  explosions  due  to  accidental  mixing  of  the  two  gases, 
and  to  guard  against  serious  results,  at  frequent  intervals  in  the  con- 
nections of  the  apparatus  and  service  pipes,  safety  devices  should  be 
inserted. 

The  common  form  of  safety  device  is  the  wire-gauze  arrangement 
of  Sir  Humphrey  Davy.  It  usually  consists  of  a  roll  of  wire  gauze  or 
a  number  of  disks  of  gauze  inserted  in  the  pipe  connections.  Such 
arrangements  sometimes  will  check  the  progress  of  an  explosion  tem- 
porarily or  completely,  but  as  a  rule  when  an  explosion  wave  passes 
along  the  pipe  in  which  the  wire  gauze  is  placed,  although  checked 
temporarily  by  the  wire-gauze  obstruction,  it  soon  heats  the  latter  to 
the  ignition  point.  Thus  the  gas  on  the  other  side  of  the  gauze  is 
ignited  and  the  explosion  wave  continues  on  its  course. 


FIG.  140. 

When  wire  gauze  is  used  preferably  it  should  take  the  form  shown 
in  Fig.  140.  A  spool  a  carries  perforations  along  its  stem  and  over 
this  wire  gauze  is  wound  to  make  a  thick  layer.  The  spool  is  placed 
in  the  holder  6  and  fitted  tightly  in  place  against  a  rubber  gasket  so 
that  gases  entering  one  end  of  b  will  pass  along  the  hollow  stem,  flow 
through  its  perforations  and  those  of  the  gauze  and  make  their  exit 
at  the  opposite  end  of  6. 

Glass  wool  obstructs  explosion  waves  in  a  fairly  satisfactory  manner 
if  it  is  inserted  into  the  pipe  connections  in  such  a  way  as  to  fill 
the  cross-sectional  area  without  being  packed  so  tightly  as  to  greatly 

590 


SAFETY  DEVICES 


591 


reduce  the  flow  of  gas.  Layers  of  glass  wool,  or  finely-divided  re- 
fractory material,  such  as  fire-brick  granules  of  about  20  mesh,  alter- 
nated with  bundles  of  wire  gauze,  may  be  packed  into  pipes  of 
relatively  large  diameter  to  form  an  excellent  safety  device,  which  is 
rendered  even  more  reliable  if  placed  in  a  tank  of  water  so  as  to  be 
kept  cool  in  event  an  explosion  wave  causes  ignition  of  the  gas  at  the 
surface  of  the  outer  layer. 

It  is  stated  by  Schoop  that  under  the  conditions  occurring  in  prac- 
tice explosion  mixtures  are  formed  when  either  gas  contains  by  vol- 
ume 6  to  8  per  cent  of  the  other  gas.  Such  an  impurity  may  quite 
readily  occur  through  injury  to  the  diaphragm  of  cells  of  the  asbestos- 
diaphragm  type,  and  in  constructions  similar  to  the  Garuti  cell  care 
should  be  taken  to  prevent  an  excess  voltage  which  will  render  the 
diaphragms  bipolar. 

Boynton's  device  for  preventing  the  transmission  of  explosions  is 
shown  in  Fig.  141.  A  is  the  gas  inlet,  B  the  outlet,  E  one  or  more 
perforated  plates  and//  a  space  filled  with  fragments  of  metal.* 


FIG.  141. 

For  the  prevention  of  hydrogen  explosions  steel  wool  is  recommended 
by  Ohmann.f  He  regards  steel  wool  as  very  suitable  to  take  up 
and  carry  off  the  heat  developed  and,  by  lowering  the  temperature 
in  this  way,  preventing  the  spreading  of  an  explosion.  To  insure 
against  the  danger  of  an  explosion,  a  roll  of  the  wool,  somewhat 
tightly  pressed  together,  is  placed  in  the  gas  conduit.  Trials  with  a 
mixture  of  f  hydrogen  and  f  air,  also  with  the  strongest  explosive 
gas  mixture  2  H  +  0,  showed  that  the  explosive  flame  or  wave  was 
checked  and  extinguished  in  contact  with  the  wool. 

*  U.  S.  Patent  58,055,  Sept.  18,  1866.  See  also  U.  S.  Patents  713,421,  730,807, 
743,064,  819,202  and  948,323. 

t  Z.  physik.  chem.  Unterricht,  11,  272;  Chem.  Zentr.  (1912),  1,  1426. 


592 


THE  HYDROGENATION  OF  OILS 


The  various  possible  causes  of  certain  fatal  accidents  resulting  from 
the  explosion  of  oxygen  or  hydrogen  cylinders  has  been  discussed  by 
Bramkamp.* 

In  most  cases  it  is  certain  that  an  explosive  mixture  of  hydrogen 
and  oxygen  has  been  introduced  into  the  cylinder.  The  two  most 

important  causes  of  this  are:  (1) 
the  use  of  the  same  compressor  al- 
ternately for  both  gases;  and  (2) 
unsatisfactory  control  and  atten- 
tion when  the  gases  are  obtained  at 
the  same  time  in  the  electrolysis 
of  water.  Other  causes  which  may 
contribute  but  which  are  unlikely 
in  themselves  to  account  for  an  ex- 
plosive mixture  in  a  full  cylinder 
are:  (1)  the  use  of  an  oxygen  cylin- 
der as  a  hydrogen  cylinder  or  vice 
versa,  without  previously  removing 
all  the  original  gas;  and  (2)  the 
absorption  of  hydrogen  by  finely- 
divided  iron  inside  the  cylinder. 
The  various  methods  by  which  the 


FIG.  142.     High-pressure  cylinders 
for  hydrogen. 


explosive  mixture  when  present 
may  be  exploded  include:  (1)  igni- 
tion of  oil  or  other  combustible 

material  in  the  valve  or  pressure  gauge  by  the  compressed  oxygen; 
(2)  local  rise  in  temperature  of  the  gas  due  to  sudden  closing  of  the 
valve;  (3)  catalytic  action  of  finely-divided  iron  in  causing  combina- 
tion in  the  mixture  and  raising  its  temperature;  and  (4)  pyrophoric 
oxidation  of  finely-divided  iron.  Bramkamp  is  of  the  opinion  that 
with  suitable  precautions  an  explosive  mixture  need  never  be  put 
into  a  cylinder,  and  that  all  cylinders  should  be  tested  by  analysis 
of  their  contents  immediately  after  filling. 

Tubes  of  compressed  hydrogen,  accidentally  contaminated  with 
air,  have  been  known  to  explode  on  connecting  them  with  a  manom- 
eter for  the  purpose  of  measuring  the  pressure  of  the  gas.  Lelarge  f 
has  found  that  if  ordinary  manometers  are  employed  in  the  usual  way, 
such  explosions  may  occur  whenever  the  hydrogen  contains  enough 
air  to  render  it  explosive,  and  the  pressure  is  sufficiently  high.  The 
reason  probably  lies  in  the  rise  of  temperature  produced  by  the  sudden 

*  Zeit.  ang.  Chem.  (1912),  536. 
t  Compt.  rend.  (1912),  914. 


SAFETY  DEVICES 


593 


FIG.  143.    Compressor  for  compressing  hydrogen  or  oxygen  into  cylinders. 


594  THE  HYDROGENATION  OF  OILS 

and  more  or  less  adiabatic  compression  of  the  air  in  the  manometer. 
Such  accidents  may  be  avoided  by  interposing,  between  the  tube  of 
compressed  gas  and  the  manometer,  a  safety-tube  containing  discs  of 
metallic  gauze  of  such  mass  that  they  are  not  appreciably  heated  by 
combustion  of  the  gas  mixture  in  the  manometer.  By  this  means  the 
ignition  of  the  main  body  of  gas  is  prevented.  Similar  safety-tubes 
should  be  employed  whenever  a  highly-compressed  explosive  gas  mix- 
ture is  allowed  to  expand  suddenly  into  a  confined  space.  Before 
measuring  the  pressure  of  compressed  hydrogen,  liable  to  contain  air 
or  oxygen,  it  is  advisable  to  determine  its  density,  as  a  further  safe- 
guard. 

SUMMARY 

The  majority  of  the  numerous  proposals  for  making  hydrogen  in 
various  ways  have  been  outlined  in  the  foregoing  for  the  reason  that 
many  investigators  at  the  present  time  are  studying  the  subject  of 
hydrogen  generation,  and  everywhere  present  and  prospective  users  of 
hydrogen  are  seeking  information  which  may  enable  a  better  under- 
standing of  the  subject. 


FIG.  144.    Pressure  tank  for  storage  of  hydrogen. 

For  oil  hydrogenation  at  least  four  methods  of  generating  hydrogen 
are  likely  to  find  a  place.  These  are  the  (1)  steam-iron,  (2)  water-gas 
liquefaction,  (3)  water-gas  and  lime  and  (4)  electrolytic  systems. 
With  the  exception  of  the  latter  these  all  require  a  water-gas  plant 
with  a  not  wholly  simple  system  of  purifiers,  etc.  As  to  the  steam- 
iron  method  it  may  be  noted  that  the  opponents  of  this  system  claim 
it  has  been  shown  in  practice  that  the  iron  sponge  will  not  regenerate 
after  a  few  operations  and  the  iron  retorts  used  are  demolished  all  too 
soon  by  the  high  heat  employed  and  have  to  be  continually  replaced. 
The  advocates  of  the  system  claim  great  improvement  in  the  matter 
of  longevity  of  the  iron  sponge  and  also  figure  on  a  cost  of  production 


SAFETY  DEVICES  595 

around  90  cents  to  $1.00  per  1000  cubic  feet  of  hydrogen.  It  is  doubt- 
ful if  this  figure  generally  could  be  reached  and  so  far  as  the  author 
can  ascertain  the  cost  in  this  country  with  plants  of  moderate  size 
is  approximately  $1.50  per  M.  The  liquefaction  system,  although 
scarcely  feasible  to  install  in  a  small  way,  should  prove  attractive  for 
large  scale  operation  as  the  cost  of  production  is  not  over  $1.00  to  $1.20 
per  M  for  gas  of  very  fair  purity.  The  objection  has  been  raised  that 
the  by-product  of  carbon  monoxide  under  high  pressure  is  dangerous 
to  handle.  The  water-gas  and  lime  system  from  the  point  of  view  of 
low  cost  of  operation  has  much  in  its  favor,  but  has  as  yet  received 
no  extensive  technical  application.  The  electrolytic  process  may  be 
called  the  foolproof  system,  as  with  proper  safeguards  against  mixing 
of  the  gases  and  suitable  safety  devices,  the  generating  plant  may  be 
operated  with  unskilled  labor.  The  objections  raised  against  it  are 
the  floor  space  required  and  the  high  cost  of  the  gas.  If,  however, 
the  oxygen  is  saved  and  compressed  it  can  usually  be  sold  at  a  profit 
which,  credited  against  the  hydrogen  account,  greatly  reduces  the  cost 
of  the  latter.  For  small  plants  electrolysis  has  much  in  its  favor.* 

PURIFICATION  OF  HYDROGEN 

In  the  previous  discussion  of  methods  of  producing  hydrogen  various 
procedures  of  purification  have  been  mentioned.  To  summarize, 

*  The  cost  of  hydrogen  per  cubic  meter  (1  cubic  meter  =35.3  cubic  feet)  pro- 
duced in  various  ways  is  given  by  Sander  (Zeitsch.  f.  angew.  Chem.  (1912),  2407) 
as  follows: 

Stationary  Plants 

Cents 
Acetylene  (Carbonium)  ...........................  ...........     3f 

Steam  (Internat.  Wasserstoff)  ................................  2£-5 

Water  gas  (Griesheim-Elektron)  ..............................  l|-2$ 

Water  gas  (Linde-Frank-Caro)  ...............................  2|-3J 

Oil  gas  (Rincker  and  Wolter)  ................................. 


Portable  Plants 

Cents 
Iron  and  sulfuric  acid  ......................................     12  J-20 

Aluminium  and  caustic  soda  ...............................  about  62$ 

Silicon  and  caustic  soda  ..........................  .........     17^-20 

Ferro-silicon  and  caustic  soda  ...............................     17^-20 

Calcium  hydride  ..........................................  about  $1.00 

Hydrogenite  (Jaubert)  .....................................  about  37  J 

Maricheau-Beaupre  system  ........................  .  .......  about  37  £ 

Activated  aluminium  (Griesheim-Elektron)  ...................  about  45 

Sachs  (Zeitsch.  f.  angew.  Chem.  (1913),  No.  94,  784)  believes  the  cheapening  of 
the  cost  of  manufacture  of  hydrogen  due  to  the  demand  for  this  gas  in  air  ship  prac- 
tice is  in  part  responsible  for  the  rapid  development  of  oil  hardening  processes. 


596  THE  HYDROGENATION  OF  OILS 

oxygen  may  be  eliminated  by  passing  the  gas  through  heated  tubes 
containing  copper  turnings;  carbon  dioxide  by  exposure  to  hydrated 
lime,  carbon  monoxide  by  contact  with  soda  lime  at  300°  C.  or  over,  in 
the  presence  of  moisture,  or  with  acid  cuprous  chloride;  and  nitrogen 
may  be  removed  by  exposure  to  heated  calcium  carbide.  Moisture 
may  be  reduced  to  a  negligible  amount  by  means  of  quicklime,  cal- 
cium chloride  or  other  desiccating  agent. 

Catalyzers  of  different  types  vary  considerably  in  their  resistance 
to  impurities  or  catalyzer  poisons  in  the  hydrogen,  but  the  period  of 
activity  of  the  more  reliable  catalyzers  is  at  best  all  too  short,  and  it 
may  be  laid  down  as  a  general  rule  that  hydrogen  free  from  moisture, 
oxygen,  sulfur,  phosphorus,  chlorine,  arsenic  and  cyanogen  compounds 
should  be  employed.  Of  course  there  are  exceptions  to  this,  as,  for 
example,  with  nickel  oxide  catalyzers  oxygen  is  thought  not  to  be 
detrimental  and  in  fact  by  some  is  regarded  as  advantageous. 

The  Badische  Anilin  und  Soda-Fabrik  *  remove  traces  of  carbon 
monoxide  from  hydrogen  by  passing  the  gases  through  caustic  alkali 
solutions  at  high  temperatures  and  pressures,  e.g.,  hydrogen  contain- 
ing 1  per  cent  of  carbon  monoxide  is  treated  with  (a)  an  80  per  cent 
solution  of  caustic  soda  at  50  atmospheres  pressure  at  260°  C.,  or  (b) 
a  25  per  cent  solution  of  caustic  soda  at  200  atmospheres  pressure  at 
240°  C.f 

Hydrogen  prepared  from  commercial  zinc  and  acid,  is  bubbled 
through  petroleum  spirit  cooled  by  liquid  air.  A  temperature  of 
110°  C.,  according  to  Renard,J  suffices  to  insure  the  removal  in  this 
way  of  all  the  arseniuretted  hydrogen  even  from  a  rapid  stream  of  the 
gas. 

Wentzki  removes  arseniuretted  hydrogen  from  impure  hydrogen 
by  passing  the  gas  upwards  through  a  cylinder  packed  with  a  mixture 
of  two  parts  of  dry  chloride  of  lime  and  one  part  of  moist  sand  or  other 
inert  material.  If  the  column  of  purification  material  be  sufficiently 
high,  the  whole  of  the  arsenic  is  retained.  A  small  quantity  of  chlorine 
is  set  free,  but  can  be  removed  by  passing  the  hydrogen  through  a 
second  cylinder  packed  with  nearly  dry  slaked  lime.§ 
*  Rabenalt  ||  purifies  hydrogen  by  passing  it  into  a  solution  of  iodine 
through  which  an  electric  current  is  simultaneously  conducted. 

*  French  Patent  439,262,  Jan.  22,  1912. 

t  By  heating  a  solution  of  caustic  alkali  under  a  pressure  greater  than  five  at- 
mospheres, hydrogen  is  freed  from  sulfur  and  sulfur  compounds.  (Badische,  British 
Patent  14,509,  June  23,  1913.) 

t  Compt.  rend.  (1903),  136  (22),  1317. 

§  Chem.  Ind.  (1906),  405. 

II  U.  S.  Patent  1,034,646,  Aug.  6,  1912. ; 


SAFETY  DEVICES 


597 


FIG.  145. 


For  purifying  electrolytic  gases  Knowles  *  uses  the  apparatus  as 
shown  in  Fig.  145.  The  gas  to  be  purified  is  first  passed  through  an 
ordinary  washer  then  through  an  explosion  trap  and  finally  enters  the 
purifier  proper.  In  its  entry  into  the  purifier  the  in-going  gas  is  pre- 
heated by  passage  around  the.  conduit  through  which  the  out-going 
gas  and  vapor  is  passing.  In  the 
purifying  chamber  the  gas  passes 
through  contact  material  and 
water  vapor  is  formed  and  is  con- 
densed and  removed.  In  the 
illustration  the  web  k  supports 
grids  /  of  porcelain  on  which 
the  contact  material  is  spread. 
Knowles  states  that  when  the 
apparatus  is  working  properly  no 
external  heat  is  required  on  ac- 
count of  the  rise  in  temperature 
caused  by  the  condensation. 

The  removal  of  sulfur  from  gas  by  the  Carpenter  process  f  involves 
passing  the  gas  over  reduced  nickel  heated  to  800°  to  900°  F.  when 
carbon  bisulfide  reacts  with  hydrogen  to  form  hydrogen  sulfide  and  the 
latter  body  is  absorbed  in  the  usual  manner. 

The  treatment  of  water  gas  to  separate  pure  hydrogen,  as  described 
by  Frank,t  is  of  interest  in  this  connection.  Water  gas,  previously 
dried  as  much  as  possible,  is  conducted  over  calcium  carbide,  at  a 
temperature  from  300°  C.  up  to  the  melting  point  of  the  carbide. 
When  water  gas  is  conducted  over  carbide  thus  heated  an  absorption 
of  all  the  substances  associated  with  the  hydrogen  takes  place.  Car- 
bon monoxide  or  dioxide  forms  with  the  carbide,  lime  or  carbonate 
of  lime  and  carbon.  The  nitrogen  is  likewise  absorbed.  The  hydro- 
carbons are  decomposed  when  passed  over  the  heated  lime-carbon 
material  with  the  separation  of  carbon.  The  action  of  the  carbide 
on  various  gases  is  indicated  by  Frank  in  the  following  reactions: 

CO  +  CaC2  =  CaO  +  3  C 
CO2  +  2  CaC2  =  2  CaO  +  5  C 
3  CO2  +  2  CaC2  =  2  CaCO3  +  5  C 
O  +  CaC2  =  CaO  +  2  C 
2N  +  CaC2  =  CaN2C  +  C 

*  U.  S.  Patent  1,073,246,  Sept.  16,  1913. 
t  Jour.  Ind.  &  Chem.  Eng.  (1914),  262. 
J  U.  S.  Patent  964,415,  July  12,  1910. 


598  THE  HYDROGENATION  OF  OILS 

SiH4  +  3  CO  +  CaC2  +  heat  =  CaSiO3  +  5  C  +  4  H 

CS2  +  CaC2  =  2  CaS  +  3  C 

H2S  +  CaC2  =  CaS  +  C2  +  H2 

zPH3  +  CaC2  =  CaP*  +  C2  +  3  zH 

CS2  +  2  C02  +  heat  =  2  S02  +  3'C 

2  S02  +  3  C  +  2  CaC2  =  CaSO4  +  CaS  +  7  C. 

Almost  chemically  pure  hydrogen  is  ultimately  obtained  as  the  final 
product.  Carbon  monoxide  or  dioxide  may  be  previously  entirely 
or  partially  removed  from  the  water  gas  by  mechanical  separation 
of  the  constituent  gases  to  relieve  the  carbide  from  the  duty  of  sepa- 
rating the  major  part  of  the  gases.  If  the  water  gas  is  produced  at  a 
high  furnace  temperature  and  contains  in  addition  to  hydrogen  almost 
exclusively  carbon  monoxide  and  only  a  little  carbon  dioxide,  the 
mechanical  separation  is  preferably  effected  by  conducting  the  water 
gas,  which  has  been  suitably  cooled,  into  a  Linde's  air-liquefaction 
machine  or  other  similarly  constructed  apparatus  to  liquefy  the  car- 
bon monoxide;  the  dioxide  and  small  quantities  of  silicon-hydrogen, 
etc.,  being  obtained  solid,  whereas  the  hydrogen  remains  gaseous  and 
can  be  separated  and  conducted  away.  If  the  water  gas  is  produced 
at  a  low  temperature,  and  if  little  carbon  monoxide  and  principally 
carbon  dioxide  are  obtained  in  addition  to  hydrogen,  the  previous 
mechanical  separation  may  be  effected  by  the  water  gas  being  cooled 
down  to  a  temperature  below  that  of  the  congealing  or  liquefying 
point  of  the  secondary  constituents  of  the  water  gas  (carbon  dioxide, 
carbon  monoxide,  etc.),  these  secondary  constituents  being  separated 
in  this  manner  in  a  solid  or  liquid  form  from  the  hydrogen  which  is 
obtained.  After  the  previous  mechanical  separation  of  the  secondary 
gases,  the  hydrogen  which  contains  some  remnant  of  other  gases,  as 
CO,  CO2,  SiH4,  H2S,  PH3,  N,  CS2,  and  hydrocarbons,  is  then  subjected 
to  a  final  purification  by  conducting  it  over  carbide.  Before  being 
passed  over  the  carbide,  the  water  gas  may  be  freed  from  carbon 
dioxide  and  monoxide  by  treatment  with  lime  and  cuprous  chloride 
solution  respectively.* 

Bosch  and  Wild  f  have  found  that  by  treating  hydrogen  under 
pressure  exceeding  five  atmospheres  with  a  hot  solution  of  fixed  caustic 
alkali,  sulphur  and  compounds  containing  sulphur  can  be  practically 
completely  removed. 

The  concentration  of  the  alkaline  solution  and  the  temperature  and  pressure 
employed  can  be  varied  within  wide  limits.  As  an  example,  caustic  soda  solution 

*  French  Patent  371,814,  Nov.  26,   1906. 

f  U.  S.  Patent  No.  1,133,087,  March  23,  1915. 


SAFETY    DEVICES  599 

of  from  10  to  50  per  cent  can  be  employed  at  a  temperature  of  from  150°  to  225°  C. 
and  a  pressure  of  fifty  atmospheres.  As  a  rule,  if  higher  pressures  be  employed, 
the  gases  can  be  passed  through  the  caustic  alkali  solution  with  a  greater  velocity 
while  still  effecting  a  total  separation  of  all  sulphur  and  sulphur  compounds. 

A  purifier  for  separating  dust  and  sulphur  compounds  from  producer  gas,  water 
gas,  and  the  like  is  described  by  Berlin  Anhaltische  Maschinenbau  *  as  follows: 
Within  and  spaced  away  from  the  wall  of  the  purifier  is  a  retort  packed  with  turnings 
of  iron  or  other  metal  capable  of  combining  with  sulphur  compounds.  Except  at 
the  two  ends  the  wall  of  the  retort  is  porous.  The  gas  enters  the  purifier,  and  passes 
through  the  porous  wall  of  the  retort,  which  retains  dust,  etc.  A  blast  of  air  may 
be  passed  into  the  purifier  to  bring  it  to  and  maintain  it  at  the  requisite  temperature 
for  the  retention  of  the  sulphur  compounds  by  the  iron  turnings. 

It  is  stated  by  the  Badische  Company  f  that  carbon  monoxide  can 
be  very  quickly  and  effectively  removed  from  gas  mixtures  by  means 
of  ammoniacal  cuprous  chloride  solution  under  pressure. 

The  solutions  contain,  in  1  liter,  considerably  more  than  60  grams  of  ammonia 
gas  in  the  form  of  free  base  or  carbonate.  Iron  apparatus  or  parts  in  motion  are 
not  injured  by  this  solution  so  that  high  pressure  can  be  employed,  where  stone- 
ware and  lead  are  not  suitable.  Ammonia  is  supplied  as  it  is  lost,  the  solution  is 
kept  in  circulation  between  the  absorption  and  a  lower  pressure  chamber  where  the 
carbon  monoxide  is  removed,  and  any  oxidation  of  copper  is  corrected  by  the  carbon 
monoxide  before  it  is  removed.  A  suitable  solution  is  prepared  by  mixing  200 
kilograms  of  cuprous  chloride,  250  kilograms  of  ammonium  chloride,  500  kilograms 
of  25  per  cent  ammonium  hydroxide  and  500  kilograms  of  water.  Operating  at 
pressures  above  100  atmospheres  very  small  amounts  of  carbon  monoxide  may  be 
removed  from  gases  (such  as  hydrogen  containing  carbon  monoxide)  in  a  short 
time. 

The  absorption  of  carbon  monoxide  from  oxygen-free  gas  mixtures  by  ammoni- 
acal cuprous  chloride  solutions  is  carried  out  by  the  Badische  Company  J  with  an 
addition  of  oxygen  to  the  gas  sufficient  in  amount  to  prevent  the  separation  of 
copper  but  not  in  such  a  quantity  as  to  cause  any  marked  oxidation  of  carbon  mon- 
oxide. 

A  method  of  freeing  gases  from  carbon  dioxide  present  as  impurity 
is  given  by  Soc.  L'Air  Liquide,§  which  consists  in  subjecting  the  impure 
gas  first  to  a  physical  purification  by  solution  under  pressure  in  water 
and  then  to  a  chemical  purification  by  the  action  of  purifying  reagent 
dissolved  in  the  water. 

The  process  is  applicable  to  the  removal  of  carbon  dioxide  from  water  gas  or 
water  gas  modified  by  catalysis  or  by  passage  over  hydrated  lime,  prior  to  lique- 
faction of  the  gas.  The  process  is  effected  by  bringing  the  compressed  gas  into 
contact  with  a  counter  current  of  water  in  a  tower,  at  the  upper  portion  of  which  is 

*  German  Patent  No.  271,122,  Dec.  12,  1912;  U.  S.  Patent  No.  1,129,558;  J.  S.  C.  I., 
1914,  472. 

t  German  Patent  No.  282,505,  Nov.  19,  1913;  Chem.  Abs.,  1915,  2299;  see  also  Brit- 
ish Patent  No.  9,271,  Apr.  14,  1914. 

t  Chem.  Abs.,  1917,  873;   Austrian  Patent  No.  72,240,  Aug.  10,  1916. 

§  British  Patent  No.  15,053,  June  23,  1914. 


600  THE  HYDROGENATION  OF  OILS 

introduced  a  small  quantity  of  a  lime  or  caustic  soda.  The  dissolved  gas  may  be 
subsequently  removed  from  the  liquid  by  relieving  the  pressure  thereon,  and,  when 
lime  is  used,  the  precipitated  carbonate  may  be  filtered  off  and  the  water  returned 
to  the  tower. 

In  a  process  for  the  absorption  of  gases  by  liquids,  under  pressure,  with  subse- 
quent regeneration  of  the  absorbent  by  relieving  the  pressure,  Ges  fur  Lindes  Eis 
maschinen  *  absorption  is  effected  under  as  high  a  pressure  as  possible  and  the 
absorbed  gas  subsequently  released  by  producing  a  partial  vacuum  in  the  absorp- 
tion vessel  and  simultaneously  passing  through  it  a  current  of  gas  in  which  the  con- 
centration of  the  absorbed  gas,  if  this  be  present,  is  lower  than  corresponds  to  its 
partial  pressure,  in  the  gas  above  the  solution.  It  is  stated  that  by  this  process 
the  absorption  of  carbon  monoxide  in  cuprous  chloride  solution,  which  hitherto 
has  proved  impracticable,  may  be  used  with  good  results,  e.g.,  for  the  production  of 
hydrogen  free  from  carbon  monoxide. 

Knowles  f  has  devised  an  apparatus  for  the  purification  of  electrolytic  gases,  con- 
sisting of  a  chamber  in  which  is  located  a  web  of  metal  or  other  material  coated 
with  a  catalytic  agent,  and  heated  either  by  electricity  or  other  suitable  means. 
The  design  is  such  that  the  gases  have  a  long  space  to  travel  in  contact  with  the 
catalytic  material  and  are  thus  well  purified. 

To  remove  oxygen  from  gaseous  mixtures,  Siemens  and  Halske  | 
pass  the  gases  over  a  metal  heated  to  incandescence,  the  metal  being 
one,  such  as  zirconium  or  titanium,  the  oxide  of  which  is  not  reduced 
by  hydrogen  or  carbon  monoxide  at  the  temperature  of  working.  In 
practice  gases  to  be  freed  from  oxygen  frequently  contain  hydrogen 
or  oil  vapors.  By  the  process  described,  it  is  stated  that  oxygen  can 
be  removed  from  such  gases  without  formation  of  steam. 

Ueno  and  Kimura  §  purify  by-product  hydrogen  by  treatment  with 
metallic  copper,  a  cuprous  salt  and  ammonium  hydroxide,  with  or 
without  the  addition  of  another  ammonium  compound.  Ueno  ||  em- 
ploys colloidal  platinum,  palladium,  iridium  or  osmium  in  an  aqueous 
vehicle  containing  an  organic  body  such  as  sugar  or  glycerine,  gum 
arabic  and  soap. 

When  working  with  hydrogen  at  raised  temperature  and  under  pressure  in  iron 
vessels,  according  to  Bosch,  <[[  if  the  iron  contains  carbon  the  strength  of  the  vessel 
suffers  to  such  an  extent  that  after  a  very  short  time  it  is  no  longer  able  to  withstand 
the  higher  pressure  which  is  being  employed,  due  to  the  action  of  the  hydrogen  upon 
the  carbon.  The  use  inside  such  iron  tube  of  a  lining  which  is  chemically  not  acted 
upon  by  hydrogen  is  of  little  value,  since,  when  high  temperatures  are  employed, 
practically  all  substances  are  pervious  to  hydrogen  under  pressure.  Although  the 
quantity  of  hydrogen  which  diffuses  through  the  walls  of  the  tube  is  only  minute 

*  German  Patent  No.  289,106,  Mar.  29,  1914;  J.  S.  C.  I.,  1916,  523. 

t  U.  S.  Patent  No.  1,073,246,  Sept.  16,  1913. 

J  German  Patent  No.  279,132,  June  28,  1913;  J.  S.  C.  I.,  1915,  230. 

§  Chem.  Abs.,  1918,  208;  Japanese  Patent  No.  31,292,  July  10,  1917. 

||  Japanese  Patent  No.  31,291,  July  10,  1917. 

f  U.  S.  Patent  No.  1,188,530,  June  27,  1916. 


SAFETY  DEVICES  601 

in  comparison  with  the  total  quantity  of  gases  treated  in  such  tube,  yet  in  course  of 
time  this  small  quantity  is  sufficient  to  act  on  the  carbon  contained  in  the  iron  of 
the  tube  to  such  an  extent  as  to  deteriorate  the  resisting  power  of  the  tube. 

Bosch  states  that  he  can  work  conveniently  with  flowing  hydrogen  under  con- 
tinuous pressure  and  at  raised  temperatures  if  the  vessel  in  which  the  reaction  is 
being  carried  out  and  within  which  the  high  pressure  is  being  maintained,  be  sur- 
rounded by  some  kind  of  structure  which  is  capable  of  supporting  the  inner  vessel, 
but  which  itself  readily  allows  any  gas  to  escape  which  may  diffuse  through  the  walls 
of  the  inner  vessel.  This  can  be  effected  by  surrounding  the  inner  vessel  with  a 
series  of  steel  rings,  or  a  suitable  network  of  bars,  or  the  inner  tube  may  be  covered 
with  a  second  tube  which  is  perforated,  the  essential  condition  being  that  the  outer 
tube,  which  is  supporting  the  inner  tube,  is  not  impervious  to  the  hydrogen  which 
diffuses  through  the  inner  tube  at  the  high  temperature  and  pressures  employed.  It 
is  most  convenient  to  construct  the  outer  perforated  tube,  network  or  rings,  of 
steel,  while  the  inner  tube,  in  which  the  hydrogen  is  contained  under  pressure 
and  heat,  may  be  constructed  either  of  steel,  or  of  some  material  which  does 
not  contain  carbon,  such  as  wrought  iron  (practically  free  from  carbon),  nickel  or 
silver. 

Reactions  in  which  hydrogen  is  involved  under  pressure  and  at  high  temperatures 
are  carried  out  in  an  apparatus  comprising  an  exterior  (metallic)  receiver,  capable 
of  supporting  the  pressure,  and  an  interior  receiver  (e.g.,  of  glazed  porcelain,  glass, 
quartz,  etc.),  capable  of  resisting  the  chemical  action  and  the  diffusion  of  the  hydro- 
gen. Or,  the  reaction  is  allowed  to  take  place  in  an  inner  metallic  or  non-metallic 
porous  receiver,  which  is  separated  from  the  outer  wall,  supporting  the  pressure,  by 
an  alloy  or  composition  capable  of  resisting  the  chemical  action  and  diffusion  of  the 
hydrogen.* 

Pier  f  describes  an  apparatus  for  effecting  reactions  with  hydrogen  under  pressure. 
To  prevent  leakage  of  hydrogen,  a  layer  of  molten  Wood's  metal  or  other  readily 
fusible  alloy  is  maintained  between  the  upper  wall  and  the  outer  casing  of  the  vessel 
(which  may  be  of  steel) .  The  inner  wall  may  be  of  porcelain  or  metal.  The  appa- 
ratus will  withstand  150  atmospheres  pressure  without  leakage. 


EFFECTS  OF  THE  PRESENCE  OF  HYDROGEN  IN  ELECTROLYTIC 

OXYGEN 

Experiments  conducted  by  the  Bureau  of  Mines  indicate  that,  at 
atmospheric  pressure,  mixtures  of  oxygen  and  hydrogen  containing 
less  than  10  "per  cent  by  volume  of  hydrogen  are  inflammable  but 
not  explosive.  Teras  and  Plenz  find  at  least  30  per  cent  of  oxygen 
is  required  for  explosion.  The  electrolytic  industry  for  making 
oxygen  and  hydrogen,  as  a  general  rule,  attains  on  an  industrial  scale 
the  generation  of  both  oxygen  and  hydrogen  at  purities  well  above 
99  per  cent.  Oxygen  containing  but  1  per  cent  of  hydrogen  is  a  non- 

*  Chem.  Abs.,  1915,  28;  French  Patent  No.  469,391  and  First  addition,  March  7,  1914. 
tU.  S.JPatent  No.  1,159,865. 


602  THE  HYDROGENATION  OF  OILS 

hazardous  product,  as  the  hydrogen  in  such  a  mixture  cannot  be 
made  to  combine  with  the  oxygen  to  produce  an  explosive  reaction. 
Hydrogen  containing  but  1  per  cent  of  oxygen  is  likewise  in  itself  a 
safe  product,  as  the  oxygen  in  such  a  mixture  cannot  be  made  to 
combine  with  the  hydrogen  to  produce  an  explosive  reaction. 

The  attention  of  the  Bureau  of  Mines  *  has  been  directed  to  a  series 
of  explosions  of  oxygen  made  by  the  electrolytic  process  in  which  life 
has  been  lost,  as  a  result  of  hydrogen  being  mixed  with  oxygen.  Rice, 
of  the  Bureau  of  Mines,  reports  that  this  is  due  to  improper  design  in 
the  manufacturing  apparatus,  i.e.,  the  cells  and  electrical  connections; 
to  insufficient  safeguards  connected  with  the  electric  apparatus,  the 
polarity  suddenly  and  unexpectedly  shifting;  to  the  manufacture  of 
oxygen  without  frequent  analyses;  and  to  incompetent  or  ignorant 
attendants.  Unfortunately,  certain  makers  of  oxygen-manufacturing 
apparatus  have  advertised  that  any  laborer  can  take  care  of  their 
apparatus.  It  is  believed  that  the  manufacture  of  electrolytic  oxygen 
can  be  carried  on  in  a  manner  to  make  it  entirely  safe.  Neverthe- 
less, certain  tanks  from  one  batch  caused  three  widely  separated  ex- 
plosions in  California,  killing  seven  men  in  all,  and  an  analysis  of  gas 
from  a  tank  filled  at  the  same  time  showed  that  it  contained  over  50 
per  cent  of  hydrogen. 

The  California  Commission  limits  hydrogen  content  in  oxygen 
containers  to  2  per  cent  after  thorough  investigation  as  to  the  cause 
of  three  explosions,  f 

Wohler  J  referring  to  the  regulations  which  have  been  enforced  in 
Germany  since  1902  with  regard  to  the  filling  and  use  of  compressed 
gas  cylinders  for  oxygen  and  hydrogen  gases,  gives  details  of  some 
recent  explosions  to  show  that  in  spite  of  all  these  precautions  accidents 
due  to  carelessness  and  negligence  are  of  frequent  occurrence. 

The  most  disastrous  of  these,  in  which  three  men  were  killed  and  many  were 
injured,  occurred  at  Darmstadt.  An  empty  oxygen  cylinder  of  210  cu.  ft.  capacity 
was  filled  with  hydrogen,  but  the  error  was  discovered  before  the  gas  was  used  and 
the  cylinder  was  returned  to  the  compressed  gas  works.  Without  emptying  the 
cylinder,  the  men  in  charge  of  the  oxygen-filling  machinery  filled  the  cylinder  to  its 
maximum  capacity  with  oxygen,  and  when  the  cylinder  arrived  at  the  railway  work- 
shops the  second  time,  and  was  put  into  use,  it  burst.  The  author  points  out  that 
owing  to  the  shortage  of  copper  the  connecting  gas  couplings  used  at  the  filling  works 
are  now  of  iron  or  steel.  The  rule  with  regard  to  right-  and  left-handed  threads  to  the 
cylinder  fittings  for  the  different  gases  is,  therefore,  easily  evaded,  for  a  steel  or  iron 
screw  may  be  externally  threaded  on  a  brass  connecting  piece  whatever  the  thread 

*  Met.  Chem.  Eng.,  1917,  402. 

t  Brownell,  Eng.  Rerord,  1917,  594. 

t  Z.  angew.  Chem.,  1917,  30,  174;  J.  S.  C.  I.,  1917,  917. 


SAFETY  DEVICES  603 

may  have  been  on  this  originally.  The  regulations  with  regard  to  the  use  of  distinc- 
tive colors  for  the  cylinders  containing  the  two  gases  have  also  been  often  ignored 
lately,  owing  to  labor  shortage  and  similar  difficulties,  and  cylinders  have  been  used 
indiscriminately  for  oxygen  or  hydrogen,  without  regard  to  their  color  or  markings. 
As  a  precaution  against  similar  accidents  and  explosions  Wohler  recommends 
the  application  of  the  Haber  test  for  explosive  gases  before  the  gas  from  any  cylinder 
is  used,  or  the  still  more  simple  soap-bubble  test,  which  consists  in  blowing  a  bubble 
with  the  gas  from  the  cylinder,  and  then  applying  a  light.  These  tests,  however,  are 
of  little  value  if  left  in  the  hands  of  the  workmen,  since  negative  results  can  easily 
be  obtained  with  them. 

Hammond  *  describes  an  apparatus  that  prevents  polarity  reversal 
by  use  of  an  automatic  switch  which  completes  the  connection  with  the 
cells  only  when  the  normal  speed  of  the  generator  is  reached.  Reversal 
of  phase  is  prevented  by  use  of  a  polarized  relay  connected  to  a  special 
shunt  which  provides  for  a  single-pole  relay  in  the  control  circuit. 
Apparatus  for  the  determination  of  purity  of  oxygen  by  absorption 
with  metallic  copper  and  of  hydrogen  by  the  combustion  method  are 
illustrated.  Causes  of  explosions  and  precautions  to  be  observed  are 
given,  f 

The  Underwriters'  Laboratories  (207  E.  Ohio  St.,  Chicago,  111.) 
have  in  preparation  Tentative  Standards  for  Oxygen  and  Hydrogen 
for  Industrial  Uses  and  for  Electrolytic  Oxygen  and  Hydrogen  Plants 
and  Their  Operation.  In  the  compilation  of  these  standards  the 
Underwriters'  Laboratories  have  had  the  assistance  of  the  Standards 
Committee  of  the  Electrolytic  Oxygen  and  Hydrogen  Association, 
formerly  Gas  Products  Association  (29  South  La  Salle  St.,  Chicago, 
111.),  and  the  Committee  on  Electrolytic  Oxygen  and  Hydrogen  of 
the  Compressed  Gas  Manufacturers'  Association  (120  Broadway, 
New  York  City),  and  after  further  revision  it  is  expected  these 
standards  will  be  adopted  by  electrolytic  oxygen  and  hydrogen  man- 
ufacturers of  this  country.  { 

*  Machinery,  23,  1070,  1917;  Chem.  Abs.,  1917,  2860. 

t  An  explosion  arrester  involving  the  use  of  a  water  seal  is  described  by  Ellis,  U.  S. 
Patent  No.  1,170,055,  Feb.  1,  1916. 

Oil-hardening  tank  explosion.  (Byrne,  Chem.  Trade  J.,  58,  164  (1916);  Chem. 
Abs.  10,  1271.)  An  explosion  occurred  May  22d,  1915,  in  one  of  six  tanks  employed  by 
Messrs.  Ardol,  Ltd.,  Selby,  Yorks,  in  converting  oil  into  a  solid  by  means  of  hydrogen. 
Each  tank  was  fitted  with  3  vertical  coils  of  copper  tubing  forming  an  endless  cir- 
cuit through  which  hot  water  was  passed.  Its  temperature  normally  was  about  290° 
and  its  pressure  2000  Ib.  per  square  inch.  The  oil  in  the  tank  was  heated  to  a  temper- 
ature of  about  260°  and  the  hydrogen,  at  a  pressure  of  5  Ib.  per  square  inch  was  sent 
from  the  bottom  upward  through  the  tank  to  the  cleansing  plant.  The  accident 
is  found  to  have  been  due  to  a  leakage  from  the  copper  coil  producing  an  unduo 
pressure  in  the  tank. 

J  J.  S.  C.  I.,  1918,  251  R. 


APPENDIX  A 

HYDROGENATED  OIL  PATENT  LITIGATION 

The  general  interest  awakened  by  litigation  in  England  over  the 
Normann  patent,  together  with  the  fact  that  the  testimony  given  has 
brought  out  much  of  interest  to  investigators  in  the  hydrogenation 
field,  has  led  to  the  inclusion  of  a  report  of  the  Court  proceedings 
which  is  here  given  substantially  as  published  in  the  British  Official 
Journal. 

IN  THE  HIGH  COURT  OF  JUSTICE. —CHANCERY  DIVISION 

Before  MR.  JUSTICE  NEVILLE 

Feb.  20  — Mar.  18,  1913 

*  JOSEPH  CROSFIELD  &  SONS  LD.  v.  TECHNO-CHEMICAL 
LABORATORIES  LD. 

Patent.  —  Action  for  infringement.  —  Admissibility  of  expert  evi- 
dence. —  Construction  of  Specification.  —  Insufficiency  of  Specification 
—  Patent  held  invalid.  —  Action  dismissed.  —  Costs  on  the  higher  scale 
allowed.  • 

In  1903  a  Patent  was  granted  for  a  ''Process  for  converting  unsaturated 
"fatty  acids  or  their  glycerides  into  saturated  compounds."  The  process 
consisted  in  treating  the  fatty  bodies  with  hydrogen  in  the  presence  of  a 
finely-divided  metal,  such  as  platinum,  iron,  cobalt,  copper,  and  espe- 
cially nickel,  adapted  to  act  as  a  catalyzer.  The  Specification  stated  that 
the  saturation  might  be  effected  by  causing  vapours  of  fatty  acid  together 
with  hydrogen  to  pass  over  the  catalytic  metal,  but  that  it  was  sufficient 
to  expose  the  fat  or  fatty  acid  in  a  liquid  condition  to  the  action  of  hydrogen 
and  the  catalyst.  The  Specification  gave  no  details  of  the  process,  but 
after  having  given,  in  general  terms,  an  example  of  the  process,  stated 
that  the  quantity  of  the  nickel  added  and  the  temperature  were  immaterial, 
and  would  only  affect  the  duration  of  the  process.  In  an  action  for  in- 
fringement of  the  Patent,  the  Plaintiffs  contended  that  the  publication  of 
the  fact  that  the  process  could  be  carried  out  with  bodies  in  the  liquid  state 

*  Supplement,  June  18,  1913.  The  Illustrated  Official  Journal  (Patents), 
Vol.  XXX.  Reports  of  Patent,  Design  and  Trade  Mark  Cases.  No.  12. 

605 


606  APPENDIX 

was  of  great  merit;  they  claimed  that  the  Patent  was  for  a  principle,  and 
that,  the  Patentee  having  shown  one  way  of  putting  it  into  practice,  he 
was  entitled  to  claim  for  all  ways.  The  Defendants  contended  that  the 
experiments  of  their  witnesses  showed  that,  for  the  success  of  the  process, 
the  catalyst  must  be  prepared  in  a  particular  way  and  the  process  carried 
out  with  precautions  not  indicated  in  the  Specification  and  requiring 
research  for  their  ascertainment. 

Held,  that  the  Patentee  claimed  the  hydrogenation  of  all  unsaturated 
fatty  acids,  and  their  glycerides,  by  the  use  of  finely-divided  platinum, 
iron,  copper,  and  cobalt,  as  well  as  nickel,  and  that  if  the  process  failed 
as  to  any  of  the  bodies  to  be  hydrogenated  or  any  of  the  catalysts  the  Patent 
was  invalid;  that  no  method  of  carrying  the  alleged  invention  into  effect 
was  sufficiently  described  in  the  Specification;  and  that  the  Patent  was 
invalid.  The  action  was  dismissed  with  costs. 

On  the  21st  of  January  1903  Letters  Patent  (No.  1515  of  1903)  were 
granted  to  Wilhelm  Normann  for  a  "  Process  for  converting  unsatu- 
"  rated  fatty  acids  or  their  glycerides  into  saturated  compounds." 

The  Complete  Specification  was  as  follows:  —  "  The  property  of 
"  finely-divided  platinum,  to  exercise  a  catalytic  action  with  hydro- 
"  gen,  as  it  does  with  oxygen,  is  already  known.  For  instance,  Wilde 
"  observed  the  following  reaction  taking  place  in  the  presence  of 
"  platinum  black:  — 

C2H2  -f-  H4  = 


"  and  Debus  noticed  the  reaction: 

"  HCN  +  H4  =  CH3NH2 

"  Recently  Sabatier  and  Sender  ens  have  discovered  that  other 
"  finely-divided  metals  will  also  exercise  a  catalytic  effect  on  hydro- 
"  gen,  viz.  iron,  cobalt,  copper  and  especially  nickel.  By  causing 
"  acetylene,  ethylene,  or  benzene  vapour  in  mixture  with  hydrogen  gas 
"  to  pass  over  one  of  the  said  metals,  the  said  investigators  obtained 
"  from  the  unsaturated  hydrocarbons  saturated  hydrocarbons,  partly 
"  with  simultaneous  condensation. 

"  I  have  found,  that  it  is  easy  to  convert  by  this  catalytic  method 
"  unsaturated  fatty  acids  into  saturated  acids.  This  may  be  effected 
"  by  causing  vapours  of  fatty  acid  together  with  hydrogen  to  pass 
"  over  the  catalytic  metal,  which  is  preferably  distributed  over  a  suit- 
"  able  support,  such  as  pumice  stone.  It  is  sufficient,  however,  to 
"  expose  the  fat  or  the  fatty  acid  in  a  liquid  condition  to  the  action 
"  of  hydrogen  and  the  catalytic  substance.  For  instance,  if  fine  nickel 
"  powder  obtained  by  reduction  in  a  current  of  hydrogen,  is  added  to 


APPENDIX  007 

"  chemically  pure  oleic  acid,  then  the  latter  heated  over  an  oil  bath, 
"  and  a  strong  current  of  hydrogen  is  caused  to  pass  through  it  for 
"  a  sufficient  length  of  time,  the  oleic  acid  may  be  completely  con- 
"  verted  into  stearic  acid.  The  quantity  of  the  nickel  thus  added 
"  and  the  temperature  are  immaterial  and  will  only  affect  the  dura- 
"  tion  of  the  process.  Apart  from  the  formation  of  small  quantities 
"  of  nickel  soap,  which  may  be  easily  decomposed  by  dilute  mineral 
"  acids,  the  reaction  passes  off  without  any  secondary  reaction  taking 
"  place.  The  same  nickel  may  be  used  repeatedly.  Instead  of  pure 
"  oleic  acid,  commercial  fatty  acids  may  be  treated  in  the  same 
"  manner.  The  yellowish  fatty  acids  of  tallow,  which  melt  between 
"  44  and  48°  C.  and  whose  iodine  number  is  35.1,  will,  after  hydro- 
"  genation,  melt  between  56.5  and  59°  C.,  while  their  iodine  number 
"  will  be  9.8  and  their  colour  slightly  lighter  than  before,  and  they 
"  will  be  very  hard. 

"  The  same  method  is  applicable  not  only  to  free  fatty  acids,  but 
"  also  to  their  glycerides  occurring  in  nature,  that  is  to  say,  the  fats 
"  and  the  oils.  Olive  oil  will  yield  a  hard  tallow-like  mass ;  linseed  oil 
"  and  fish  oil  will  give  similar  results. 

"  By  the  new  method,  all  kinds  of  unsaturated  fatty  acids  and  their 
"  glycerides  may  be  easily  hydrogenised.  It  is  not  necessary  to 
"employ  pure  hydrogen  for  the  purpose  of  the  present  invention; 
"  commercial  gas  mixtures  containing  hydrogen,  such  as  water  gas, 
"  may  also  be  used." 

The  Patentee  claimed:  —  "  1.  The  process  for  converting  unsatu- 
"  rated  fatty  acids,  or  their  glycerides,  into  saturated  compounds, 
"  which  consists  in  treating  the  said  fatty  bodies  with  hydrogen  in  the 
"  presence  of  a  finely-divided  metal  adapted  to  act  as  a  catalyser, 
"  substantially  as  described.  2.  The  herein  described  manufacture 
"  of  saturated  fatty  compounds  from  unsaturated  fatty  acids,  or  their 
"  glycerides,  by  means  of  water  gas  or  similar  gas  mixtures." 

On  the  19th  of  December,  1911,  Joseph  Crosfield  &  Sons  Ld.  com- 
menced an  action  for  infringement  of  the  Patent  against  Techno- 
Chemical  Laboratories  Ld.  and  Nils  Testrup,  claiming  the  usual  relief. 

The  Plaintiffs  by  their  Statement  of  Claim  alleged  that,  (1)  they 
were  the  owners  of  the  Patent;  (2)  the  Patent  was  valid  and  subsisting; 
(3)  the  Defendants  had  infringed  and  threatened  and  intended  to 
infringe. 

By  their  Particulars  of  Breaches  they  alleged  that,  (1)  the  Defend- 
ants had  infringed  by  importing  into,  and  by  the  manufacture,  sale, 
offering  for  sale,  supply  and  use  in,  this  country  of  compounds  made 
in  accordance  with  the  process  described  in  the  Specification  and 


608  APPENDIX 

claimed  in  both  the  Claims,  and  by  the  use  in  this  country  of  the  proc- 
ess; and  (2),  in  particular,  the  Defendants,  and  each  of  them,  had, 
on  the  1st  of  December,  1911,  caused  to  be  treated  with  hydrogen  in 
the  presence  of  a  finely-divided  metal  adapted  to  act  as  a  catalyser, 
in  their  factory  situate  at  "  Fairlawn,"  Clapham  Park,  in  the  county 
of  London,  9  kilogrammes  of  cotton  oil,  in  infringement  of  both  the 
Claims. 

By  their  Defence  the  Defendants,  (1)  did  not  admit  the  allegations 
in  paragraph  1  of  the  Statement  of  Claim;  (2)  denied  that  they,  or 
either  of  them,  had  infringed  or  threatened  or  intended  to  infringe; 
and  (3)  said  that  the  Patent  was,  and  always  had  been,  null  and  void. 

By  their  amended  Particulars  of  Objections  they  said  that,  (1) 
Wilhelm  Normann  was  not  the  true  and  first  inventor.  (2)  The  alleged 
invention  was  not  subject-matter  for  a  valid  Patent,  by  reason  of  the 
common  and/or  public  knowledge  at  the  date  of  the  Patent.  The 
Defendants  would  refer  to  all  the  prior  publications  set  out  in  para- 
graph 4  below  as  disclosing  part  of  the  public  knowledge.  (3)  The 
alleged  invention  was  not  useful.  (4)  The  alleged  invention  had  been 
published  in  this  realm  prior  to  the  date  of  the  Patent:  —  (i)  By  the 
deposit  in  the  Patent  Office  Library  of  the  following  Specifications: 
(a)  British:  —  Lake  (No.  2798  of  1883)  and  Ramage  (No.  7242  of  1901). 
(6)  German:  —  Zurrer  (No.. 62,407).  The  whole  of  each  of  the  Speci- 
fications was  relied  upon,  (ii)  By  the  sale  and  publication  in  the 
United  Kingdom,  and  by  the  deposit  in  the  Patent  Office  Library,  of 

(c)  "  Comptes  Rendus  de  P  Academic  des  Sciences,"  of  Paris,  vol.  133, 
dated   1901,   pages  321-4,   comprising  an  article  entitled   "  Chimie 
"  Organique.  —  Nouvelle  methode  de  preparation  de  F  aniline  et  des 
"  alcalis  analogues."     Note  de  MM.  Paul  Sabatier  et  J.  B.  Senderens. 

(d)  "  Bulletin  de  la  Societe  de  Chimie,"  series  3,  vol.  1,  pages  295-6, 
comprising  a  communication  entitled  "  No.  29.  —  Transformation  de 
"  Tacide  oleique  en  acide  stearique  "  by  De  Wilde  and  Reychler.     (e) 
"  Journal  of  the  Chemical  Society,"  London,  for  the  year  1889,  vol. 
56,  part  2,  page  1140,  comprising  an  abstract  of  the  communication 
of  De  Wilde  and  Reychler.     (f)  "  Watts's  Dictionary  of  Chemistry," 
edition  1892,  vol.  3,  page  637,  column  2,  lines  42-4.     (g)  "  Sitzungs- 
"  berichte  der  Kaiserlichen  Akademie  der  Wissenschaften/'  Vienna, 
1876,  vol.  72,  part  II,  pages  366-75,  comprising  a  paper  by  Guido  Gold- 
schmiedt,   entitled   "  Uber  die  Umwandlung  von  Sauren  der  Reihe 
"  CnH2n-2O2  in  solche  der  Reihe  CnH2nO2.     (5)  The  Complete  Speci- 
fication of  the  Patent  did  not  particularly  describe  and  ascertain  the 
nature  of  the  invention  and  in  what  manner  the  same  was  to  be  per- 
formed, and  was  insufficient  and/or  misleading  in  the  following  par- 


APPENDIX  609 

ticulars: —  (a)  No  useful  result  could  be  obtained  by  following  the 
directions  given  in  the  Specification.  (6)  No  process  was  described 
by  which,  as  alleged,  saturation  of  unsaturated  fatty  acids,  or  their 
glycerides,  could  be  easily  or  at  all  effected,  (c)  No  process  was  de- 
scribed by  which  fatty  acids,  or  their  glycerides,  could  be  hydroge- 
nised  by  the  action  of  catalytic  iron,  copper,  cobalt,  nickel  or  platinum. 
(d)  No  process  was  described  whereby  hydrogenation  of  fatty  acids, 
or  their  glycerides,  could  be  effected  without  the  formation  of  secondary 
products,  (e)  No  process  was  described  whereby  any  useful  results 
could  be  obtained  by  the  use  of  any  of  the  finely-divided  metals  men- 
tioned. (/)  No  process  was  described  whereby  fatty  acids,  or  their 
glycerides,  could,  as  suggested,  be  hydrogenised  by  treatment  in  a 
vaporised  condition,  (g)  The  treatment  as  described  of  oleic  acid  in 
the  liquid  condition  did  not  result  in  complete  saturation,  as  alleged, 
or  in  any  practical  or  substantially  useful  saturation,  (h)  No  suffi- 
cient directions  were  given  as  to  the  quality  of  catalyst,  or  the  tem- 
peratures or  times  required  to  produce  the  alleged  results,  or  as  to 
what  variations  of  those  factors  might  be  required  for  different  cata- 
lysts, and  those  factors  were  not  immaterial  as  to  the  alleged  results. 
(i)  The  same  catalyst  could  not  be  used  repeatedly  as  described  at 
page  2,  lines  40  to  41.  Alternatively,  no  sufficient  directions  were 
given  to  enable  the  same  catalyst  to  be  used  repeatedly,  (j)  No  useful 
result  could  be  obtained  by  the  use  of  commercial  gas  mixtures  as 
described  on  page  3,  lines  5  and  6.  (k)  No  sufficient  directions  were 
given  as  to  the  preparation  of  nickel  or  other  metal  to  be  used  as 
catalyst.  (I)  The  statement  on  page  3,  lines  3  and  4,  of  the  Specifica- 
tion, namely,  that  by  the  new  method  all  kinds  of  unsaturated  fatty 
acids  and  their  glycerides  might  be  easily  hydrogenised,  was  incorrect. 
(m)  No  sufficient  directions  were  given  as  to  which  impurities  might 
be  present  with,  .or  as  to  which  impurities  must  be  excluded  from,  the 
hydrogen  in  order  that  the  process  might  be  carried  out. 

By  their  further  and  better  Particulars  the  Defendants  alleged  that 
as  to  paragraph  5  (I)  of  their  Particulars  of  Objections,  the  following 
would  not  be  easily  or  at  all  hydrogenised :  —  Olive,  linseed,  fish, 
whale,  rape,  and  cottonseed  oils,  or  any  fatty  oils;  oleic,  erucic,  linolic, 
linoleic,  and  ricinoleic  acids,  or  any  unsaturated  fatty  acids,  by  treat- 
ment in  a  vaporised  or  liquid  condition  by  the  alleged  new  method. 
And  they  alleged  as  to  paragraph  5  (m)  that  the  following  impurities 
must  be  excluded  from  the  hydrogen  in  order  that  the  latter  could,  by 
any  process,  hydrogenise  fatty  acids  or  their  glycerides:  —  Sulphur, 
sulphuretted  hydrogen,  and  all  other  volatile  sulphur  compounds, 
arsenic,  arseniuretted  hydrogen  and  all  other  volatile  arsenic  com- 


610  APPENDIX 

pounds,  phosphorus,  phosphoretted  hydrogen  and  all  other  volatile 
phosphorus  compounds,  chlorine,  oxygen,  the  oxides  of  nitrogen, 
ammonia,  and  empyreumatic  substances  obtained  in  the  production 
of  water  gas. 

Upon  an  application  by  the  Plaintiffs  for  further  and  better  Particu- 
lars as  to  paragraph  5  (7),  the  Defendants  alleged  that  no  fatty  oils 
and  no  unsaturated  fatty  acid  could  be  easily  or  at  all  hydrogenised 
in  a  vaporised  or  liquid  condition  by  the  Plaintiffs'  process,  and  stated 
that  they  did  not  intend  to  offer  any  evidence  of  specific  instances 
other  than  those  specified  in  the  Particulars. 

In  their  Answers  to  Interrogatories  the  Defendant  Company  stated 
that,  on  the  occasion  of  the  visit  of  the  Patentee  to  the  Defendant 
Company's  premises  at  Fairlawn,  Clapham  Park,  on  the  1st  of  De- 
cember, 1911,  to  inspect  a  process  for  the  hardening  of  fats,  there  was 
used  a  cylindrical  autoclave  1  metre  high  and  f  metre  in  diameter 
(inside  measurements),  with  a  steam  jacket,  and  fitted  with  a  non- 
conducting lining  of  unknown  material.  Nine  kilograms  of  cotton  oil 
were  pumped  into  the  autoclave,  and  288  grams  of  a  composition, 
containing  a  catalytic  agent  calculated  on  the  oil,  was  used  and  was 
mixed  with  the  oil  prior  to  the  introduction  of  the  mixture  into  the 
autoclave.  The  autoclave  was  then  filled  with  hydrogen  from  a 
cylinder  to  a  pressure  of  15  atmospheres.  During  the  operation,  the 
pressure  varied  from  time  to  time  according  to  the  absorption  of 
hydrogen.  A  mechanically  driven  circulation  pump  was  connected 
with  the  autoclave  both  by  its  suction  and  delivery  conduits.  By 
means  of  a  pump  and  a  jet  for  spraying,  a  mixture  of  oil  and  composi- 
tion containing  the  catalytic  agent  was  drawn  from,  and  forced  back 
into,  the  autoclave.  The  iodine  absorption  was  not  determined.  The 
composition  containing  the  catalytic  agent  was  prepared  from  a  salt 
of  nickel.  The  Defendant  Company  said  that  the  catalyst  was  the 
subject  of  provisional  protection  (No.  4702  of  1912),  and  they  ob- 
jected to  giving  further  particulars,  but  subsequently  they  said  that 
the  composition  was  prepared  as  follows:  —  About  1^  kilograms  of 
nickel  sulphate  was  dissolved  in  about  3  litres  of  water,  and  about  the 
same  weight  of  sodium  carbonate,  dissolved  in  about  the  same  quan- 
tity of  water,  and  at  about  70-80°  C.,  was  added  to  the  nickel  sulphate 
which  was  at  about  60-70°  C.  The  mixture  was  stirred  for  about 
1J-2  hours,  and  the  precipitate  was  filtered  off  and  washed  with  dis- 
tilled water  at  about  25°  C.  for  60-70  hours  alternately  in  tanks  and 
filter  press.  A  small  sample  was  dried  and  tested  to  ascertain  that 
the  precipitate  had  been  sufficiently  washed.  The  washed  precipitate 
was  dried  in  hot  air  at  80-85°  C.,  and  was  calculated  to  weigh  720 


APPENDIX  611 

grams.  It  was  then  roasted  in  an  iron  frying  pan  for  about  15  minutes 
over  an  open  Bunsen  gas  burner,  and  the  weight  after  roasting  was 
calculated  to  be  about  380  grams.  The  product  was  heated  to  about 
300°  C.  for  about  6  minutes  in  a  current  of  hydrogen  in  revolving  glass 
tubes  slightly  inclined,  the  precipitate  being  introduced  at  the  higher 
end  and  through  a  spiral  glass  tube,  and  the  hydrogen  at  the  lower  end. 
The  product,  which  weighed  288  grams,  was  directly  introduced  into  a 
small  quantity  of  oil,  which  was  mixed  with  the  9  kilos  the  following 
day. 

The  Defendants  during  the  trial  referred  to  the  following  papers:  - 
Moissan,  Oxides  of  nickel  ("  Annales  de  chimie  et  de  physique,"  1880, 
5th  series,  vol.  21,  page  238)  —  the  exhibit  A.L.  9;  Moissan  and 
Moureu,  Action  of  acetylene  on  iron,  &c.  ("  Comptes  Rendus,"  1896, 
vol.  122,  1st  half  year,  page  1240)  —  the  exhibit  A.L.  9;  Sabatier  and 
Senderens  in  the  "Comptes  Rendus"  (the  exhibit  A.L.  5),  Action  of 
nickel  on  ethylene  (124  (1897),  page  616);  Action  of  nickel  on  ethyl- 
ene:  synthesis  of  ethane  (ib.,  page  1358);  Hydrogenation  of  acetylene 
in  the  presence  of  nickel  (128  (1899),  page  1173);  Action  of  copper  on 
acetylene;  formation  of  a  very  condensed  hydrocarbon,  cuprene  (130 
(1900),  page  250);  Hydrogenation  of  acetylene  in  the  presence  of 
copper  (ib.,  page  1559);  Hydrogenation  of  acetylene  in  the  presence 
of  reduced  iron  or  cobalt  (ib.,  page  1628);  Hydrogenation  of  ethylene 
in  the  presence  of  various  reduced  metals  (ib.,  page  1761);  Hydro- 
genation of  acetylene  and  ethylene  in  the  presence  of  divided  platinum 
(131  (1900),  page  40);  Action  of  various  divided  metals,  platinum, 
cobalt  and  iron,  on  acetylene  and  ethylene  (ib.  (1900),  page  267); 
Direct  hydrogenation  effected  in  the  presence  of  reduced  nickel;  prepa- 
ration of  hexahydrobenzene  (132  (1901),  page  210);  General  method  of 
synthesis  of  the  naphthenes  (ib.  (1901),  page  566);  Hydrogenation  of 
various  aromatic  hydrocarbons  (ib.,  page  1254);  new  method  of  pre- 
paring aniline  and  analogous  alkalies  (133  (1901),  page  321);  direct 
hydrogenation  of  carbon  oxides  in  the  presence  of  various  divided 
metals  (134  (1902),  page  689);  Hydrogenation  of  ethylenic  hydro- 
carbons by  the  contact  method  (ib.,  page  1127);  Synthesis  of  various 
petroleums:  contribution  to  the  theory  of  the  formation  of  natural 
petroleums  (ib.,  page  1185);  Direct  hydrogenation  of  acetylenic  hydro- 
carbons by  the  contact  method  (135  (1902),  page  87);  Direct  hydro- 
genation of  oxides  of  nitrogen  by  the  contact  method  (ib.,  page  278) ; 
and  a  paper  by  the  same  authors  in  the  "Annales  de  chimie,"  &c.,  8th 
series,  vol.  4  (1905),  page  5  —  an  exhibit  marked  J.L.  1. 

Sir  A.  Cripps  K.C.  for  the  Plaintiffs.  —  The  Plaintiffs  are  substan- 
tially Brunner,  Mond  &  Co.,  and  the  real  Defendants  are  Lever  Bros. 


612  APPENDIX 

Ld.  An  important  feature  of  the  invention  is  that  it  has  enabled  fish 
oils,  and  particularly  whale  oil,  to  be  used  for  soap-making,  hardening 
it  and  destroying  its  smell.  Before  the  Patent,  it  was  not  known  that 
the  catalytic  hydrogenation  of  fatty  acids  or  oils  could  be  effected 
without  alteration  of  the  quantity  of  oxygen  contained  in  the  acids  or 
oils.  The  Patentee  did  not  discover  any  new  method  of  using  catalysts, 
but  he  used  them  successfully  with  bodies  with  which  they  had  never 
been  used  before;  and  he  found  that  catalysts  could  be  used  with  sub- 
stances, that  could  not  be  readily  vaporised,  by  simply  treating  them 
in  the  liquid  state.  That  had  been  thought  impossible.  It  is  alleged 
that  the  directions  given  in  the  Specification  are  insufficient,  but  the 
Patent  is  for  a  principle  of  wide  scope  and  there  is  no  need  for  minute 
directions,  because  the  process  will  work  under  all  conditions.  The 
invention  has  effected  a  revolution  in  the  soap-making  industry,  and 
the  Patent  is  a  master  Patent.  The  Specification  describes  a  way  of 
putting  the  principle  into  practice.  Lake's  Specification  deals  merely 
with  the  extraction  of  glycerine  from  fatty  substances,  and  has  no  bear- 
ing on  the  invention  here;  nor  has  Ramage's  Specification,  which 
relates  only  to  the  drying  of  oils,  without  any  hydrogenation.  Ziirrer's 
process  is  merely  for  saturating  fatty  acids  with  chlorine,  and  then 
replacing  the  chlorine  by  hydrogen  by  heating  under  pressure  with 
water  and  metals;  there  is  no  catalytic  action.  Sabatier  and  Senderens 
state  generally  the  catalytic  action  of  certain  finely-divided  metals  in 
adding  hydrogen  to  incomplete  organic  molecules,  and  then  go  on  to 
deal  with  the  substitution  of  hydrogen  for  oxygen.  The  Patentee's 
object  is  to  keep  the  oxygen  in  the  acids  and  oils,  and  to  add  hydrogen, 
and  Sabatier  would  lead  people  away  from  that.  The  papers  by  De 
Wilde  and  Reychler  and  Goldschmiedt  do  not  deal  with  catalytic  proc- 
esses at  all.  The  Defendants  allege  non-utility,  meaning  that  if  the 
Patentee's  directions  are  followed  the  result  that  he  describes  would 
not  be  obtained.  Several  of  the  allegations  in  paragraph  5  of  the 
Particulars  of  Objections  are  mere  general  allegations  that  the  Paten- 
tee's process  will  not  work.  Catalytic  action  was  well  known,  and  it 
was  not  necessary  to  give  directions  as  to  the  mode  of  preparation  of 
the  catalysts.  The  claim  is  for  the  application  of  known  catalytic 
methods  to  substances  to  which  they  had  not  been  applied  before  — 
for  obtaining  an  old  product  by  a  new  method.  The  Patentee  men- 
tions nickel  as  a  catalyst,  as  being  the  best  metal  for  the  purpose.  A 
competent  chemist  would  have  no  difficulty  in  finding  what  were  the 
best  temperatures  and  proportions. 

Evidence  was  given  in  support  of  the  Plaintiffs'  case. 

Dr.  A.  Liebmann  stated  that  fats  could  not  be  vaporized.     There 


APPENDIX  613 

was  nothing  in  literature  as  to  anyone,  prior  to  the  date  of  the  Patent, 
having  acted  with  hydrogen  as  a  catalyzer  on  a  liquid;  Sabatier  had 
said  the  presence  of  the  liquid  was  fatal  and  destroyed  the  catalyst. 
The  liquid  oils,  after  having  been  hardened  and  made  into  fats  by 
the  patented  process,  could  be  used  for  various  purposes.  In  the 
case  of  the  fish  oils  the  disagreeable  smell  was  destroyed,  and  cheap 
vegetable  oils  could  be  used  for  the  manufacture  of  margarine,  and 
oils  could  be  rendered  useful  for  soap-making  or  candle-making.  Be- 
fore 1903  it  was  known  that  it  was  impossible  to  obtain  a  vapour  of 
a  glyceride,  and  that  a  fatty  acid  could  be  distilled  in  super-heated 
steam,  or  under  reduced  pressure.  Steam  would  probably  oxidise 
the  catalyst  unless  hydrogen  was  present,  and  it  would  be  excluded 
from  vaporisation.  The  witness  had  used  a  current  of  hydrogen  for 
the  vaporisation  of  fatty  acids.  He  gave  details  of  experiments  he 
had  successfully  made  in  the  application  of  the  patented  process. 

Dr.  F.  W.  Passmore  stated,  inter  alia,  that  the  great  part  of  the 
invention  was  that  it  had  shown  the  erroneous  character  of  the  old 
theory  that  anything  that  would  tend  to  cover  up  the  surface  of  the 
catalyst  would  destroy  it,  and  had  shown  that  it  was  possible  to 
catalyse  in  fat. 

Sir  James  Dewar  also  gave  evidence. 

Walter  K.C.  summed  up  the  Plaintiffs'  case.  —  Moissan  and  Moureu 
in  1896  dealt  with  the  action  on  a  mixture,  of  acetylene  and  hydro- 
gen, of  iron,  nickel  and  cobalt  prepared  by  reduction  with  hydrogen 
at  as  low  a  temperature  as  possible.  They  found  that,  when  incan- 
descence took  place,  part  of  the  acetylene  was  polymerised,  and  part 
was  split  up.  Their  theory  was  that  the  porous  state  of  the  metal 
led  to  the  condensation  of  the  acetylene,  and  the  evolution  of  heat, 
and  that  all  bodies  having  that  catalytic  or  pyrophoric  structure 
must  give  an  identical  result.  They  referred,  as  to  the  precautions 
to  be  taken  in  obtaining  the  nickel,  to  the  paper  by  Moissan  in  the 
"  Annales  de  Chimie,"  1880.  Dr.  Passmore  said  that  he  found  in- 
structions to  obtain  the  hydrated  oxide  of  nickel  in  a  finely-divided 
state  by  precipitation  from  the  nitrate,  sulphate,  or  carbonate,  and 
that  the  finely-divided  nickel,  obtained  from  that  oxide  by  reduction 
at  as  low  a  temperature  as  possible,  would  be  pyrophoric  and  de- 
compose acetylene.  Sabatier  .and  Sender  ens  continued  Moissan' s 
work,  and,  in  their  Papers  on  the  action  of  nickel  on  ethylene,  said 
that  the  reaction  takes  place  with  the  catalytic  nickel,  with  nickel 
reduced  at  a  red  heat,  or  even  with  nickel  filings.  Then  they  dealt  with 
the  conversion  of  ethylene  into  ethane  by  means  of  hydrogen  and  a 
catalytic  agent.  After  that,  they  dealt  with  the  hydrogenation  of 


614  APPENDIX 

acetylene  in  presence  of  nickel,  and  with  the  action  of  copper  and  of 
iron  and  cobalt  on  acetylene,  and  with  the  hydrogenation  of  ethylene 
in  presence  of  various  reduced  metals,  with  the  hydrogenation  of 
benzene,  and  with  the  preparation  of  aniline  from  nitro-benzene  and 
analogous  nitro-bodies.  The  results  show  that  it  is  impossible  to 
say  that  the  method  that  will  act  in  some  cases  will  act  in  others,  or 
to  see  why  the  fatty  acids  do  not  wet  or  act  upon  the  surface  so  as 
to  inhibit  the  action  of  the  catalyst.  Nowhere  throughout  those 
Papers  is  there  any  work  with  other  than  pyrophoric  bodies,  except 
in  the  case  of  acetylene  and  ethylene.  Normann  continued  the 
work.  He  referred  to  the  literature  telling  how  to  prepare  the  cata- 
lysts, although  he  need  not  have  done  so,  as  the  literature  was  part 
of  the  common  stock  of  knowledge  of  chemists.  He  stated  that  the 
fatty  acids,  not  their  glycerides,  may  be  treated  in  the  vaporised 
condition.  There  is  no  mystery  as  to  the  method  of  converting  them 
into  vapours.  It  is  a  common  operation  to  bubble  hydrogen  through 
a  liquid,  and  get  the  vapour  of  the  liquid  mixed  with  hydrogen.  And 
Sabatier  described  that  method,  and  also  the  use  of  a  capillary  tube. 
Then  came  Normann's  great  discovery,  that  the  fatty  acids,  and  their 
glycerides,  could  be  treated  in  the  liquid  condition.  The  explanation 
seems  to  be  that  the  liquid  does  not  wet  the  metal,  just  as  oil  will 
stick  to  metal  and  not  to  rock,  and  so  float  up  the  metal.  As  to  the 
use  of  an  oil-bath,  that  appliance  is  used  when  the  temperature  de- 
sired is  from  about  100°  to  250°.  All  the  experiments  conducted  at 
temperatures  between  these  limits  succeeded.  No  chemist  would 
endeavour  to  obtain  finely-divided  nickel  by  first  grinding  the  oxide. 
In  some  of  the  Defendants'  experiments  the  oxide  from  which  the 
nickel  was  obtained  was  ground;  it  ought  to  have  been  precipitated  — 
grinding  will  not  give  the  fineness  required. 

Astbury  K.C.  for  the  Defendants.  —  The  precipitated  oxide  dries 
into  a  hard  cake,  that  has  to  be  ground.  There  is  no  evidence  that 
Normann's  process  is  useful.  The  solidification  of  oils  in  this  coun- 
try is  only  now  coming  into  commercial  use.  An  ordinary  chemist 
might  work  on  Normann's  process  for  years,  and  obtain  no  useful 
result  at  all.  The  Specification  is  deficient  as  to  any  valuable  direc- 
tions, and  is  misleading.  To  obtain  a  useful  result  something  must 
be  done  that  is  not  even  hinted  at  in  the  Specification  or  in  Sabatier' 's 
papers.  A  catalyst  that  will  work  with  one  sample  of  some  particu- 
lar fatty  acid  or  glyceride  will  not  work  with  another  sample.  The 
whole  matter  is  mysterious.  Sabatier  did  not  use  the  pyrophoric 
metal  used  by  Moissan,  and  the  Specification  ought  to  have  given 
directions  on  the  point.  The  Specification  may  be  construed  as 


APPENDIX  615 

saying  that  fats  may  be  treated  in  the  vaporised  state,  though  it  is 
sufficient  for  them  to  be  treated  in  the  liquid  condition;  and  it  is  ad- 
mitted that  fats  cannot  be  vaporised.  The  nickel  used  by  the  De- 
fendants has  been  obtained  by  the  ordinary  process  of  reduction  in 
hydrogen,  and,  if  that  is  not  sufficient,  the  Patent  is  invalid  for  in- 
sufficiency of  the  Specification.  The  Patentee  says  the  temperature 
is  immaterial,  but  no  one  has  used  a  temperature  below  100°,  and 
some  of  Sabatier's  processes  take  place  in  the  cold.  If  Normann  had 
tried  besides  nickel,  iron,  cobalt,  and  copper,  he  would  have  found 
out  certain  differences  between  their  action  and  that  of  nickel,  and 
in  that  case  he  ought  to  have  disclosed  the  best  method  of  carrying  out 
the  process.  He  says  that  water-gas  may  be  used;  that  means  com- 
mercial water-gas,  which  contains  sulphuretted  hydrogen  and  cannot 
be  successfully  used.  The  Claim  is  for  applying  catalysis  to  the  fatty 
bodies  by  vaporising  or  by  the  liquid  process.  The  Plaintiffs'  wit- 
nesses state  that  if  one  makes  reduced  nickel  by  the  processes  described 
in  the  text-books  one  will  fail,  and  Dr.  Liebmann  went  so  far  as  to  say 
that  one  would  probably  fail  if  one  bought  nickel  oxide  in  a  shop  and 
reduced  it  as  told  by  Sabatier.  The  Plaintiffs  say  their  case  stands  or 
falls  on  being  able  to  confine  their  Patent  to  preparing  the  catalyst 
by  the  particular  method  described  in  Sabatier's  and  Moissan's  papers. 
But  Moissan  describes  the  reduction  of  the  hydrated  sesquioxide  of 
nickel  obtained  by  the  action  of  chlorine  on  the  hydrate  of  nickel 
protoxide  and  neither  Sabatier  nor  Normann  suggests  that  it  is  neces- 
sary to  use  the  oxide  prepared  in  that  way.  The  use  of  chlorine 
would  "  poison  "  the  catalyst.  The  Plaintiffs  say  that  the  nickel,  to 
be  catalytic,  must  be  pyrophoric,  but  pyrophoric  nickel  will  not  act 
in  some  cases.  For  some  unexplained  reason,  it  will  harden  one 
sample,  say,  of  linseed  oil,  but  not  another  sample.  The  action  de- 
pends on  the  mode  of  preparation  of  the  body  from  which  the  oxide 
is  made,  on  something  in  the  fatty  body,  and  on  the  temperature. 
Sabatier  is  actually  misleading,  as  he  did  not  say  that  it  is  material 
how  the  oxide  is  made,  and  he  did  not  say  anything  about  the  mode 
of  preparing  the  bodies  from  which  the  oxide  is  obtained.  Mr.  Bal- 
lantyne  followed  Normann,  Sabatier,  and  Moissan  and  failed  in  every 
case.  Then  he  had  a  suggestion  from  the  Defendant  Testrup,  not 
given  by  the  Plaintiffs'  authorities,  and  in  some  cases  he  succeeded 
and  in  some  he  failed.  He  had  found  a  similar  result  in  repeating 
Dr.  Passmore's  experiments.  Iron  with  acetylene  is  very  pyrophoric, 
but  iron  as  a  catalyst  for  hydrogenation  is  practically  useless;  it  will 
not  act  at  all  with  liquids.  The  temperature  at  which  the  catalyst 
is  prepared  is  immaterial  except  as  to  acetylene.  Sabatier  said  that 


616  APPENDIX 

the  catalytic  decomposition  of  ethylene  takes  place  very  well  if  the 
nickel  has  been  reduced  at  a  red  heat,  and  in  that  case  it  is  not 
pyrophoric.  But  the  nickel  is  not  so  active  as  if  it  had  been  reduced 
at  300°,  which  is  not  Moissan's  temperature.  A  chemist  reading 
Sabatier's  Papers  would  conclude  that  the  density  of  the  nickel  is  not 
increased  by  higher  temperature,  whether  it  is  partly  in  the  reduction 
or  in  the  next  process.  Sabatier  says  the  nickel  must  be  freshly  re- 
duced; the  Defendants  have  always  freshly  reduced  theirs.  He  says 
that  acetylene  can  be  hydrogenised  by  sheet  copper.  There  is  not  a 
single  suggestion  in  Sabatier's  Papers  that  one  is  to  reduce  from  a 
hydrate,  and  from  a  body  that  itself  has  been  prepared  at  a  low  tem- 
perature, and  still  less  is  there  any  suggestion  that  the  temperature 
of  reduction  in  any  case  should  be  Moissan's  240°,  instead  of  300°. 
The  Specification  is  capable  of  being  construed  as  meaning  that  the 
vapour  process  is  applicable  to  the  fats  as  well  as  to  the  fatty  acids, 
that  the  expression  "  fatty  acids,"  when  used  alone,  stands  both  for 
the  acids  and  their  glycerides,  the  fats.  The  Patentee  either  knew, 
or  did  not  know,  that  Sabatier's  method  would  not  act,  that  it  was 
necessary  to  adopt  Moissan's  method  of  reduction  from  a  higher 
oxide  at  a  low  temperature,  and  that  the  hydrate,  instead  of  the 
oxide,  must  be  used.  If  he  knew  any  one  of  those  three  matters, 
which  are  essential  to  success,  he  has  not  mentioned  them;  if  he  did 
not  know  them,  then  he  has  not  made  an  invention.  And,  even  if 
the  catalyst  is  prepared  by  the  Plaintiffs'  method,  with  certain  of  the 
fats  and  fatty  bodies,  no  result  is  obtained.  To  infringe  a  master 
Patent  by  the  use  of  an  equivalent,  the  equivalent  must  be  known  at 
the  date  of  the  Patent  to  be  an  equivalent.  In  1903  it  was  not  known 
that,  in  acting  catalytically  on  a  liquid,  it  was  equivalent  to  bubbling 
hydrogen  through  the  liquid  to  take  a  fatty  body  and  the  metal  and 
spray  them  into  a  chamber  containing  hydrogen  under  pressure,  for 
it  is  admitted  that  no  catalysis  of  a  liquid  was  known  at  all,  and  none 
of  the  witnesses  knew  of  any  process,  catalytic  or  other,  in  which  the 
metal  and  body  were  sprayed  together,  or  any  liquid  with  metal  in 
suspension  in  it  was  sprayed  into  a  gas  under  pressure.  That  is  an 
invention  of  Testrup,  and  will  give  results  that  the  Patentee's  process 
will  not  give.  The  Patentee  says  that  temperatures  are  unimportant; 
Sabatier  says  they  are  most  important;  they  vary  greatly  with  each 
catalyst  and  body  acted  on;  it  is  impossible  to  get  any  general  law 
out  of  Sabatier  at  all.  There  is  no  evidence  that  the  patented  process 
has  ever  been  worked. 

Evidence  was  given  in  support  of  the  Defendants'  case. 

H.  Ballantyne,  in  answer  to  questions  dealing  with  the  point  whether 


APPENDIX  617 

a  chemist  would  know  that  by  obtaining  nickel  oxide  through  the 
hydroxide  by  precipitation,  he  would  get  the  oxide  in  a  more  porous 
form,  stated  that  a  chemist  could  get  the  oxide  in  a  bulky  but  finely- 
divided  state,  and  that  he  would  know  that  he  would  have  a  more 
finely-divided  material  than  if  he  went  to  a  higher  temperature.  The 
witness  said  that,  as  to  specimens  of  nickel  reduced  from  the  oxide 
and  nickel  reduced  from  the  carbonate,  the  latter  would  be  more 
bulky,  and  more  finely-divided,  but  would  have  a  larger  particle; 
the  two  specimens  could  both  be  sufficiently  rapidly  permeated  by  a 
gas,  and  the  denser  of  the  two  would  have  better  pyrophoric  proper- 
ties than  the  other,  but  pyrophoric  activity  was  independent  of  cata- 
lytic activity;  in  the  case  of  the  hydrogenation  of  oil  one  is  dealing 
with  a  liquid  getting  into  a  porous  body.  When  the  nickel  oxide  was 
reduced,  nickel  would,  by  the  removal  of  the  oxygen,  be  left  in  a 
cavernous  condition,  though  there  might  be  some  contraction. 

0.  Hehner  stated,  that  he  had  made  a  series  of  experiments  —  in 
which  he  used  the  purest  oleic  acid,  and  2  per  cent  of  the  most  active 
nickel  reduced  at  360°  from  purest  nickel  oxide  for  three  hours.  The 
rate  of  hydrogen  flow  was  about  14  litres  per  hour,  and  the  depth  of 
the  oil  column  4  inches  and  the  width  If  inches.  The  temperatures 
throughout  the  respective  experiments  were  90°,  100°,  120°,  and  150°. 
The  original  iodine  absorption  was  86.4  per  cent.  After  18  hours 
10  minutes,  it  was  reduced  in  experiment  (3)  to  85.1  and  in  (4)  to 
81.7,  in  (5)  to  82.9,  and  in  (6)  to  61.8;  and  in  the  last  experiment,  after 
57  hours  5  minutes,  it  was  reduced  to  45.5. 

Dr.  Julius  Lewkowitsch  stated,  that  before  1903  he  had  read 
Sabatier's  earlier  Papers  and  had  tried  to  hydrogenate  oleic  acid,  as 
vapour  and  as  liquid,  with  nickel;  but  had  failed.  He  had  prepared 
the  nickel  by  converting  the  sulphate  into  carbonate,  converting  that 
into  oxide,  and  reducing  the  oxide  at  400°  or  a  little  above.  Then  he 
had  read  the  Specification,  but  had  again  failed.  Later  he  had  read 
Sabatier's  Paper  of  1905  and  had  succeeded  after  two  years'  work. 

0.  Hehner,  recalled,  stated,  that,  in  preparing  the  nickel  he  used, 
he  had  made  the  green  hydroxide,  and  treated  it  with  chlorine,  obtain- 
ing Mdissan's  sesquioxide. 

Dr.  A.  Liebmann,  recalled,  stated  in  cross-examination,  that  he 
had  made  a  number  of  further  experiments.  For  one,  he  had  bought 
nickel  protoxide,  reduced  it  at  300°-320°  C.,  and  used  it  for  the 
hydrogenation  of  oleic  acid  and  had  succeeded. 

Jenkins  K.C.  summed  up  the  Defendants  case.  —  The  Patent  is 
invalid,  first,  because  the  Patentee  claims  a  process  for  converting 
unsaturated  fatty  acids  into  saturated  compounds  by  a  catalytic 


618  APPENDIX 

method  applied  to  the  vapours  of  the  fatty  acids,  which  process  is  not 
useful;  secondly,  because  he  claims  a  process  for  converting  unsat- 
urated  fatty  acids,  or  their  glycerides,  into  saturated  compounds  by 
a  catalytic  method  applied  to  the  vapours  of  the  glycerides,  which 
process  is  impossible;  thirdly,  because  he  claims  the  substitution  of 
commercial  gas  mixtures  for  hydrogen  in  carrying  out  his  processes, 
whereas  the  use  of  those  gas  mixtures  renders  the  processes,  if  other- 
wise practicable,  impracticable  unless  the  mixtures  are  purified,  and 
he  gives  no  directions  for  their  purification;  fourthly,  because  he 
claims  a  catalytic  method  wherein  metals  other  than  nickel,  and  par- 
ticularly iron,  cobalt,  copper,  and  platinum,  are  employed  as  the 
catalysers,  which  processes  are  impossible  or  impracticable;  or,  alter- 
natively, the  Specification  is  insufficient  and  misleading  in  that  no 
sufficient  directions  are  given  as  to  the  catalytic  substance  necessary 
to  be  employed  to  enable  the  invention  to  be  carried  out;  and,  fifthly, 
because  the  Specification  is  insufficient  in  that  no  sufficient  directions 
are  given  to  enable  the  invention  to  be  performed  so  far  as  the  same 
relates  to  the  processes  claimed  for  the  conversion  of  unsaturated 
fatty  acids  or  their  glycerides  in  a  liquid  condition  into  saturated  com- 
pounds. The  first  four  reasons  depend  to  a  great  extent  upon  con- 
struction, and  do  not  involve  much  dispute  as  to  facts.  If  any  one  of 
them  is  valid,  it  is  possible  that  the  Patent  might  be  made  good  by 
amendment,  but  if  the  fifth  reason  —  the  broad  attack  —  is  valid 
then  the  Patent  could  not  be  made  good  by  any  amendment.  If  the 
Defendants  succeed  on  any  one  of  these  points  they  are  entitled  to 
have  the  action  dismissed.  The  first  objection  assumes,  for  the  pur- 
pose of  argument,  that  the  Specification  tells  how  the  process  can  be 
carried  out,  but  asserts  that  when  carried  out  it  is  useless.  As  to  the 
vapour  process,  the  Patentee  seemed  not  to  know  that  the  fats  cannot 
be  vaporized,  as,  in  1912,  he  applied  for  a  Patent  in  the  Transvaal 
and  said  in  his  Declaration  that  the  glycerides  might  be  exposed  in  a 
vaporised  condition  to  the  action  of  the  hydrogen  and  catalyst.  With 
regard  to  the  use  of  commercial  gas,  which  is  the  subject  of  a  separate 
Claim,  Sabatier  removed  the  sulphuretted  hydrogen  that  would  be  fatal 
to  the  process,  but  the  Patentee  gives  the  impression  that  purifica- 
tion is  not  necessary.  The  Defendants  have  shown  that  one  cannot, 
by  using  iron,  cobalt,  copper  or  platinum  as  catalysts,  bring  about 
the  hydrogenation.  The  Plaintiffs'  witnesses  say  that  they  have 
effected  the  hydrogenation  with  iron,  cobalt  and  copper  in  the  vapour 
process;  but  the  Defendants  have  shown  that  one  cannot  succeed 
with  these  metals  or  platinum  in  the  liquid  process.  If  the  Patentee 
claims  hydrogenation  in  the  liquid  process  by  a  metal  other  than  nickel, 


APPENDIX  619 

the  Patent  is  invalid.  With  regard  to  platinum  black,  the  Plaintiffs 
have  not  shown  that  it  will  work  with  anything.  They  say  that  it  is 
not  material,  that  is  a  question  of  construction;  and  the  Defendants 
say  that  the  Claim  includes  finely-divided  platinum.  As  to  the  gen- 
eral scope  of  the  Specification,  the  expression  "  this  catalytic  method  " 
means  the  use  of  the  finely-divided  metals  to  exercise  a  catalytic 
action  with  hydrogen  as  they  did  with  oxygen.  The  Plaintiffs  seemed 
to  think  that  Sabatier's  Papers  were  to  be  treated  as  if  the  Patentee 
had  recited  them,  but  that  is  a  false  construction.  He  did  not  recite 
them,  but  he  recited  prior  knowledge  so  far  as  was  known  to  him,  and 
exhaustively,  as  he  mentions  platinum  black,  and  makes  it  clear  that 
he  may  include  platinum  sponge.  Then  he  gives  general  directions 
that  it  is  sufficient  to  expose  the  fat  or  fatty  acid,  in  a  liquid  condition, 
to  the  action  of  hydrogen  and  the  catalytic  substance.  That  is  the 
Patentee's  claim.  It  is  not  narrowed  by  what  follows.  The  Patentee 
has  thrown  his  net  very  widely,  and  has  taken  a  correspondingly 
heavy  burden.  He  thought  he  had  discovered  a  new  principle,  and 
had  found  that  the  supposed  capriciousness  of  catalytic  action  did 
not  exist.  The  Plaintiffs  have  been  working  on  this  subject  for  years, 
but  they  have  not  told  the  Court  what  they  have  been  doing.  It  is 
difficult  to  avoid  reading  their  subsequently-acquired  knowledge  into 
the  knowledge  of  1903.  It  may  be  said  that  the  Patentee  has  pre- 
scribed, in  a  loose  way,  a  range  of  temperature  from  100°  to  250°  — 
the  range  of  an  ordinary  oil-bath;  but  he  has  stated  that  the  reaction 
will  be  obtained  at  100°  with  every  body  treated.  And,  as  he  says 
that  temperature  is  immaterial,  he  has  not  purported  to  give  any  range 
of  temperature.  The  Plaintiffs  have  to  choose  between  saying  that 
the  statement  that  temperature  is  immaterial  is  of  general  application, 
in  which  case  the  Patent  is  clearly  bad,  and  saying  that  the  direction 
merely  refers  to  the  instance  given,  of  nickel,  and  that  the  statement 
means  that  having  found  a  temperature  at  which  the  reaction  is 
obtained,  it  is  immaterial  whether  or  not  one  goes  higher.  The  in- 
stance, and  the  direction  as  to  the  oil-bath  are  not  of  the  essence  of 
the  invention.  It  has  been  proved  that  the  temperature  and  the 
proportions  are  vital.  As  to  the  water-gas,  if  one  purifies  it,  one  does 
something  that  makes  the  hydrogen  operative,  and  so  the  process 
comes  within  Claim  1.  If  the  words  "  temperature  is  immaterial  " 
are  of  general  application  to  the  Specification,  they  are  misleading 
and  invalidate  the  Patent;  if  they  refer  only  to  the  specific  instance 
then  the  Specification  is  insufficient  as  to  the  general  process.  The 
differences  of  opinion  between  the  experts  have  been  narrowed  down 
to  the  mode  of  preparation  of  the  catalyst  —  the  nickel.  Mr.  Hehner 


620  APPENDIX 

used  temperatures  of  about  300°  for  the  reduction  of  the  oxide,  and 
sometimes  went  to  340°;  Dr.  Liebmann  went  as  high  as  360°  in  one 
case.  The  question  is  further  narrowed  down  to  the  preparation  of 
the  oxide.  The  process  can  be  carried  out  with  finely-divided  metal 
obtained  from  any  oxide,  but  only  with  certain  bodies,  and  with  cer- 
tain precautions.  Moissan's  Papers  have  no  bearing  on  the  matter. 
His  Paper  of  1880  was  simply  directed  to  the  investigation  of  the 
allotropy  of  certain  oxides.  The  experiments  of  the  Plaintiffs' 
witnesses  had,  in  order  to  succeed,  to  be  conducted  with  special 
stirring  apparatus  and  a  strong  current  of  hydrogen,  precautions  that 
are  not  indicated  by  the  Patentee.  The  failure  of  Dr.  Lewkowitsch 
to  obtain  Normann's  results,  although  following  his  Specification  care- 
fully, shows  that  the  Specification  is  insufficient.  The  Patentee 
assumed  that  the  catalyst  that  would  act  with  the  gases  would  act 
with  the  liquids,  and  it  turned  out  that  it  would  not.  As  to  infringe- 
ment, the  Defendants'  method  is  an  improvement  on  the  Patentee's, 
and  if  his  claim  is  limited  to  his  precise  description,  it  is  not  an  equiv- 
alent. 

Sir  A.  Cripps  K.C.  replied.  —  As  to  the  knowledge  at  the  date  of  the 
Patent,  the  references  to  Sabatier  imply  a  reference  to  Moissan,  and 
Sabatier  says  that  the  best  method  is  to  prepare  the  catalyst  in  the 
way  described  by  Moissan,  that  is,  in  order  to  get  a  porous  oxide, 
hydrate  should  be  used.  The  Plaintiffs'  witnesses  went  through  the 
sesquioxide  and  the  hydrate  to  the  protoxide,  and  showed  that  the 
process  worked  best  in  that  way.  They  tried  further  experiments 
with  oxides  made  from  the  carbonate,  sulphate,  and  nitrate,  and  suc- 
ceeded. The  invention  is  of  enormous  value;  it  is  said  to  be  worth 
a  quarter  of  a  million  a  year;  and  there  can  be  no  question  as  to  utility, 
or  as  to  the  sufficiency  of  the  statement  of  the  invention.  The  only 
question  is  as  to  the  sufficiency  of  the  directions.  The  stirrer  and  the 
strong  current  of  hydrogen  used  by  the  Plaintiffs'  witnesses  were 
expedients  such  as  would  naturally  be  adopted  by  a  chemist  wishing 
to  get  contact  between  the  reagents.  Supposing  the  invention  to 
be  the  hydrogenation  of  unsaturated  fatty  acids,  and  oils  so  as  to 
saturate  them,  and  the  Patentee  gives  one  example  that  works,  that 
is  sufficient.  Possible  complications  with  different  catalysts  have 
nothing  to  do  with  the  matter.  With  regard  to  the  presence  of  sul- 
phuretted hydrogen  in  water-gas  or  illuminating  gas,  a  chemist  would 
know  that  sulphur  is  a  "  poison  "  to  the  catalyst  and  would  remove 
it  from  the  water-gas,  and  it  is  not  found  in  modern  illuminating  gas. 
The  direction  that  the  catalyst  is  to  be  finely  divided  is  sufficient  to 
indicate  that  it  is  to  be  as  finely  divided  as  possible.  The  use  in  the 


APPENDIX  621 

Claim  of  the  expression  "  adapted  to  act  as  a  catalyst  "  has  been 
objected  to,  but  such  a  description  is  properly  employed  in  a  claim 
for  a  wide  principle.  The  further  experiments  of  Dr.  Liebmann  and 
Dr.  Passmore  were  conducted  in  accordance  with  the  directions  given 
in  the  Specification.  They  started  with  a  fine  nickel  powder  obtained 
by  reduction  in  a  current  of  hydrogen,  added  to  it  oleic  acid,  as  pure 
as  possible,  heated  it  over  an  oil  bath  and  passed  a  strong  current  of 
hydrogen  through  it,  so  as  to  keep  the  metal  in  a  state  of  suspension. 
They  succeeded,  and  the  only  objection  made  is  that  they  added 
stirring,  but  that  is  an  expedient  that  would  naturally  and  properly 
be  adopted. 

Neville  J.  —  The  Specification  in  the  present  case  is  short  and  in- 
artificial. The  Patentee  discloses,  I  think,  clearly  enough  what  he 
claims  to  have  discovered.  It  was,  in  the  first  instance,  that  the  satu- 
ration by  hydrogen  or  hydrogenation  of  unsaturated  fatty  acids  and 
their  glycerides,  fats  and  oils,  could  be  attained  by  catalysis.  In  in- 
troducing his  discovery,  he  refers  to  the  fact  that  it  had  already  been 
disclosed  that,  in  certain  cases,  catalytic  action  with  hydrogen  had 
been  brought  about  by  the  presence  of  finely-divided  platinum,  and 
further  that  Sabatier  and  Senderens  had  extended  discovery  in  this 
direction  by  showing  that  other  finely-divided  metals,  namely,  iron,  co- 
balt, copper,  and  especially  nickel,  might  take  the  place  of  platinum. 
He  tells  us  that  Sabatier  —  I  will  use  this  name  as  including  Senderens 
—  obtained  saturated  hydrocarbons  from  unsaturated  hydrocarbons 
(partly  with  simultaneous  condensation,  which  I  take  to  mean  what 
he  calls  later  secondary  reactions),  namely,  acetylene,  ethylene,  or 
benzene,  by  causing  their  vapours  mixed  with  hydrogen  gas  to  pass 
over  one  of  the  said  metals.  Reading  the  Specification  as  a  whole,  I 
think  he  then  proceeds  to  tell  us  that  his  discovery  is  that  it  is  easy  by 
"  this  catalytic  method  "  -  which  means,  I  think,  hydrogenation  by 
catalysis  —  to  hydrogenise  all  kinds  of  unsaturated  fatty  acids  and 
their  glycerides,  that  is  to  say,  fats  and  oils.  I  may  say,  in  passing, 
that  the  glyceride  is  merely  the  fatty  acid  with  the  addition  of  gly- 
cerine, and  the  fats  and  oils,  thus  composed,  differ  from  the  fatty  acids 
in  this  respect,  that  while  fatty  acids  may,  under  certain  conditions 
be  vaporised,  fats  and  oils  cannot.  How  to  vaporise  a  fatty  acid  the 
Specification  does  not  tell  us,  but  Normann  says  that  hydrogenation 
of  the  unsaturated  fatty  acid  may  be  obtained  by  causing  it  in  vapour 
with  hydrogen  to  pass  over  the  catalytic  metal.  This  vaporisation, 
however,  he  declares  to  be  unnecessary,  since  it  is  sufficient  to  expose 
the  fat  or  fatty  acid  —  that  is  to  say,  any  unsaturated  fatty  acid  or  its 
glyceride  —  in  a  liquid  condition  to  the  action  of  hydrogen  and  the 


622  APPENDIX 

catalytic  substance.  The  evidence  shows  the  advantage  of  treating 
the  fats  and  fatty  acids  in  the  liquid  state  without  vaporisation  to  be 
very  great,  and  I  think  Normann  did  not  intend  to  indicate  vaporisa- 
tion as  part  of  his  process,  but  to  point  out  that  you  could  obtain  hydro- 
genation  by  a  far  simpler  method.  To  dismiss  this  point  at  the  outset, 
I  do  not  think,  upon  any  construction  of  the  Specification,  that  the 
difficulty  of  vaporisation,  even  if  it  were  as  great  as  the  Defendants 
suggest,  would  avoid  the  Patent.  If  the  Specification  is  sufficient  in 
other  respects,  what  Normann  here  says  is  true,  and,  even  if  the  proc- 
ess by  vaporisation  is  of  no  commercial  value,  the  liquid  process  is, 
and  I  think  the  Patent  would  stand.  Having  told  us  that  treatment 
in  the  liquid  state  suffices,  Normann  discloses  an  instance  in  which  he 
alleges  that  pure  oleic  acid  may  be  completely  converted  into  stearic 
acid,  that  is,  a  non-saturated  fatty  acid  into  a  saturated  fatty  acid. 
I  think,  if  he  has  described  a  process  by  which  this  may  be  done,  and 
if  that  process  is  effective  with  all  fats  and  oils  and  all  other  fatty  acids 
in  combination  with  any  "  finely-divided  metal  adapted  to  act  as  a 
catalyser  "  (including  platinum,  iron,  cobalt,  copper,  and  nickel),  the 
Specification  would  be  sufficient.  Indeed,  I  should  be  inclined  to  hold 
that,  if  the  invention  was  substantially  co-extensive  with  the  Claim, 
proof  that  some  fatty  acid  or  oil  could  not  be  successfully  treated  by 
one  or  more  of  the  catalysers  mentioned  was  immaterial,  so  long  as  the 
exception  was  of  no  commercial  importance. 

There  are  minor  points  upon  the  construction  of  the  Specification 
raised,  such  as  the  possibility  of  using  commercial  gas  mixtures  as  a 
substitute  for  hydrogen,  but  I  will,  in  the  first  instance,  examine  the 
question  of  whether  the  process  which  Normann  describes  will  effect 
the  result  which  he  claims  for  it,  and  I  will  here  say  that,  if  by  his  proc- 
ess a  substantial  saturation  is  effected,  sufficient  for  technical  pur- 
poses, I  should  not  consider  its  failure  to  ensure  complete  saturation 
fatal,  notwithstanding  that  he  has  stated  that  the  oleic  acid  may  be 
completely  converted  into  stearic  acid;  nor  should  I  think  it  fatal  if 
some  secondary  reaction  took  place,  notwithstanding  his  declaration 
to  the  contrary,  so  long  as  such  reactions  did  not  substantially  interfere 
with  the  utility  of  the  process. 

In  my  judgment,  the  right  of  a  Patentee  to  his  monopoly  is  essen- 
tially a  matter  of  substance,  and  the  question  to  be  decided  a  broad 
one,  namely,  whether  he  has  in  substance  given  the  consideration 
which  the  grant  of  the  Patent  requires. 

Now  let  us  turn  to  Normann's  Specification  and  see  what  are  the 
conditions  to  be  fulfilled  to  obtain  the  result  which  he  indicates.  First 
of  all,  nickel  powder  obtained  by  reduction  in  a  current  of  hydrogen  is 


APPENDIX  623 

to  be  procured.  There  is  no  special  meaning,  I  think,  to  be  attached 
to  the  word  "  powder/'  except  that  the  product  is  to  be  in  a  fine  state 
of  division;  but  the  evidence  shows  that,  if  metallic  nickel  is  to  be 
obtained  by  reduction,  it  must  be  obtained  by  reduction  of  the  oxide; 
so  we  take  nn'ely-divided  nickel  obtained  by  reduction  of  nickel  oxide 
in  hydrogen  and  add  it  to  chemically  pure  oleic  acid.  For  pure  oleic 
acid,  we  may  substitute  any  commercial  fatty  acid,  or  fat,  so  far  as  the 
method  is  concerned;  though,  of  course,  if  we  do,  we  cannot  expect 
complete  conversion  of  the  whole  compound,  inasmuch  as  impurities 
may  be  expected.  Then  the  oleic  acid  is  to  be  heated  over  an  oil-bath. 
No  temperature  is  mentioned.  The  ordinary  temperatures  for  which 
oil-baths  are  used  are  variously  stated  as  extending  from  50°  or  100°  to 
250°  C.,  but,  inasmuch  as  the  inventor  tells  us  immediately  after  that 
the  quantity  of  nickel  added  and  the  temperature  are  immaterial  and 
will  only  affect  the  duration  of  the  process,  I  think  it  is  impossible  to 
construe  the  Specification  as  giving  any  direction  as  to  the  temperature 
to  be  employed,  unless,  perhaps,  one  may  say  that,  as  heating  is 
directed,  it  should  be  something  above  room  temperature  —  how  much, 
I  think,  one  does  not  learn.  A  strong  current  of  hydrogen  is  to  be 
passed  through  the  mixture,  and  I  think  it  is  common  ground  that  the 
current  should  be  strong  enough  to  keep  the  metallic  nickel  suspended 
in  the  liquid  in  order  to  give  the  opportunity  of  contact  between  the 
surface  of  the  nickel  and  the  molecules  of  the  other  bodies. 

Before  proceeding  further,  I  will  put  in  untechnical  language  what 
I  understand  from  the  evidence  to  be  conveyed  by  the  word  "  catal- 
ysis." It  appears  that  in  the  presence  of,  or  in  contact  with,  certain 
metals,  chemical  bodies  undergo  changes  which  do  not  otherwise  take 
place.  The  reactions  induced  by  the  presence  of  the  catalyst  may 
involve  merely  the  splitting  up  of  a  single  chemical  body,  of  which  the 
decomposition  of  acetylene  in  the  presence  of  finely-divided  nickel  is 
an  instance,  or  the  combination  of  two  chemical  bodies  which,  but 
for  contact  with  the  catalyst,  would  have  retained  their  composition 
unchanged,  although  in  contact  with  one  another.  The  hydrogeha- 
tion  of  a  fatty  acid  where  hydrogen  and  the  fatty  acid  are  brought 
into  contact  in  the  presence  of  a  suitable  catalyst  is  an  instance  of  the 
latter  kind  of  reactions,  and  that  which  forms  the  subject-matter 
of  the  present  invention. 

To  return  to  the  Specification,  the  experiments  made  by  Mr. 
Ballantyne  and  Mr.  Hehner  show  that  you  may  take  finely-divided 
nickel,  or  nickel  powder,  obtained  by  reduction  from  the  oxide  in  a 
current  of  hydrogen,  and  add  it  to  pure  oleic  acid  or  any  other  fatty 
acid,  warm  the  mixture,  and  pass  through  it  a  strong  current  of  hydro- 


624  APPENDIX 

gen,  without  obtaining  the  catalytic  reaction  indicated  by  the  Paten- 
tee at  all.  That,  by  preparing  your  nickel  powder  in  a  special  way 
and  raising  the  temperature  to  a  certain  degree,  you  may  obtain  the 
result  required,  although  the  reaction  appears  to  be  very  capricious, 
is  shown  by  the  experiments  of  Dr.  Liebmann  and  Dr.  Passmore  and 
admitted  by  Mr.  Ballantyne.  The  Plaintiffs'  contention  is  that  the 
success  of  Dr.  Liebmann  and  Dr.  Passmore  is  conclusive  to  establish 
the  validity  of  the  Patent,  for  it  is  said  that  these  gentlemen  did  no 
more  than  the  Specification  directed.  They  say  that  it  was  known 
in  1903  that  catalysis  was  a  surface  or  contact  action,  and  that,  for 
the  purpose  of  obtaining  contact,  the  finer  the  division  the  better  the 
chance,  and  that  it  was  known  that,  for  the  purpose  of  catalysis,  the 
oxide  should  be  reduced  to  the  metal  at  the  lowest  possible  temper- 
ature, or  at  about  300°  C.  Therefore,  they  say  that  any  competent 
chemist  upon  reading  the  Specification  would,  as  of  course,  take 
nickel  oxide  as  finely-divided  as  possible,  and  reduce  it  in  hydrogen 
at  a  temperature  of  from  300°  to  350°. 

I  pause  here  to  state  certain  conclusions  at  which  I  have  arrived 
upon  the  evidence.  It  appears  that  the  fineness  of  division  of  the 
nickel  —  by  which  is  meant  the  minuteness  of  the  pieces  composing 
the  substance,  depends  —  not  upon  the  temperature  (within  the 
ranges  of  temperature  which  are  dealt  with  here)  at  which  the  oxide  is 
reduced  to  the  metal,  but  upon  the  physical  state  of  the  oxide  with 
regard  to  minuteness  of  division  at  the  time  when  the  reduction  com- 
mences, the  number  of  pieces  of  metal  after  the  reduction  being  sub- 
stantially the  same  as  the  number  of  pieces  in  the  oxide.  Therefore, 
the  temperature  at  which  the  reduction  takes  place  is  in  this  connec- 
tion immaterial.  The  activity  of  a  catalyst  does  not,  however,  I 
think,  depend  solely  upon  minuteness  of  division,  but  upon  the  po- 
rosity of  the  pieces  of  metal  composing  the  powder.  In  the  course  of 
reduction,  when  the  oxide  gives  up  its  oxygen,  the  metal  left  behind 
is  in  a  porous,  or  what  has  been  described  as  a  cavernous  condition, 
the  result  being  that,  inasmuch  as  the  fatty  substance  may  be  able 
to  penetrate  into  the  cavities,  a  greater  surface  is  afforded  for  contact 
than  if  it  were  in  a  denser  or  more  solid  condition.  This  distinction 
has,  I  think,  not  been  sufficiently  regarded  in  some  parts  of  the 
evidence,  the  words  "  finely-divided  "  having  been  sometimes  used 
to  denote  porosity,  rather  than  the  smallness  of  the  pieces  into  which 
the  metal  is  divided.  Mr.  Ballantyne,  explaining  the  different  quali- 
ties required  for  pyrophoric  purposes  and  catalytic  purposes,  speaks  of 
metal  in  larger  particles  or  grains  being  more  finely-divided  than  metal 
in  smaller  particles  or  grains.  I  do  not  think  that,  in  fact,  the  words 


APPENDIX  025 

"  finely-divided  "  have  a  meaning  in  chemistry  different  from  that 
which  they  bear  in  English.  The  effect  of  heating  is  to  cause  the 
porous  metal  to  contract  and  become  denser;  hence  the  desirability 
of  reducing  the  oxide  at  a  low  temperature;  and  I  think  to-day  it 
would  be  common  ground  that  the  most  promising  catalyst  for  hydro- 
genation  would  be  a  suitable  metal  in  the  highest  state  both  of  fine 
division  and  porosity.  At  the  same  time,  it  must  be  remembered  that 
this  so-called  catalysis  remains  unexplained.  All  that  is  known 
about  it  is,  that  it  happens,  and  no  one  can  safely  predict  what  will 
happen  in  any  case  not  already  tested  by  experiment.  Nothing 
seemed  more  unlikely  before  Normann's  discovery  than  that  this  cata- 
lytic method  should  be  available  for  the  saturation  of  fats  and  oils. 

Papers  by  Moissan  and  Sabatier  are  relied  upon  by  the  Plaintiffs 
in  two  ways :  first,  because  Sabatier  is  referred  to  in  the  Specification, 
and  Moissan  is  referred  to  by  Sabatier,  and  it  is  said  that  this  is  an 
express  reference  by  the  Patentee  adding  to  the  information  given 
by  the  Specification  all  the  information  to  be  gleaned  from  these 
Papers,  and  in  them,  it  is  said,  are  to  be  found  directions  how  to  pre- 
pare your  catalysts  for  Normann's  invention;  and,  secondly,  it  is 
said  that,  at  all  events,  what  was  contained  in  them  was  public  knowl- 
edge, and  the  hypothetical  competent  chemist  was  bound  to  supple- 
ment the  Specification  with  the  knowledge  acquired  from  Sabatier. 

The  first  contention  is,  in  my  judgment,  untenable.  It  may  per- 
haps be  permissible  for  a  Patentee  to  say  in  his  Specification:  —  "  For 
"  the  purpose  of  carrying  my  invention  into  effect,  I  refer  you  to  such 
"and  such  a  publication  in  which  you  will  find  all  necessary  directions." 
I  doubt  if  this  would  fulfil  his  obligations  to  the  public,  but,  at  all 
events,  on  turning  to  the  publication  indicated,  you  must  find  in  clear 
and  precise  terms  the  very  process  which  he  claims,  or  one  which, 
without  further  experiment,  can  be  applied  for  the  carrying  into  effect 
of  his  invention.  To  turn  the  hypothetical  chemist  loose  into  the 
labyrinth  of  long  chemical  papers  dealing  with  a  variety  of  subjects 
more  or  less  connected  with  the  matter  in  hand,  and  tell  him  to  search 
for  himself  and  adopt  for  the  purposes  of  the  invention  what  he 
deems  applicable,  would  be  to  fall  altogether  short  of  his  duty  as 
patentee.  On  the  question  of  common  knowledge,  I  think  there 
must  be  shown  something  more  than  the  fact  that  there  has  been 
recently  published  information  which,  though  not  directed  to  the 
matter  in  hand,  ought,  if  properly  understood  and  digested,  to  have 
led  the  inquirer  to  adopt  certain  methods  and  precautions  in  carry- 
ing out  the  invention  with  regard  to  which  the  Specification  is  silent. 
But  further,  if  every  line  of  Moissan  and  Sabatier  were  read,  I  do  not 


626  APPENDIX 

think  it  would  lead  the  inquirer  to  suppose  that  any  particular 
method  of  preparing  the  oxide  for  the  purposes  of  Normann's  process 
was  necessary,  nor  indeed,  as  the  experiments  show,  was  it.  Mois- 
san's  Paper  is  a  description  of  an  isolated  demonstration  of  the  reduc- 
tion of  a  sesquioxide  of  nickel  prepared  in  a  particular  way  through 
various  transformations  down  to  metallic  nickel,  and  is  referred  to  by 
Sabatier  in  a  Paper  but  remotely  bearing  upon  Normann's  invention. 
It  is  true  that  Moissan  declares  that  the  resulting  metallic  nickel  will 
be  pyrophoric,  but  it  appears  to  me  that  there  is  no  direct  connection 
between  a  metal  being  pyrophoric  (that  is,  being  in  a  state  in  which 
it  will  oxidise  in  ordinary  temperature  at  a  white  heat)  and  being  a 
catalyst  which  can  be  relied  upon  to  realise  successfully  Normann's 
invention.  Indeed,  the  fact  that  some  of  the  catalysts  used  by  Mr. 
Ballantyne  and  Mr.  Hehner  in  unsuccessful  experiments  were  pyro- 
phoric, seems  conclusive  on  this  point.  I  think,  therefore,  the  question 
of  how  to  prepare  a  finely-divided  metal  so  that  it  may  be  pyrophoric 
is  not  relevant  to  the  present  case. 

I  come  to  the  conclusion,  upon  the  evidence,  that  Normann's 
process  will  not  produce  the  result  he  claims  for  it  unless  the  fine  nickel 
powder  is  obtained  in  a  special  manner  not  indicated  by  the  Specifica- 
tion, or  unless  a  very  strong  current  of  hydrogen  is  used,  and  mechan- 
ical stirring  or  some  other  special  device  is  resorted  to.  The  possible 
effect  of  violent  agitation  in  keeping  the  surface  of  the  catalyst  free 
from  the  poison  of  the  oil  is  pointed  out  by  Mr.  Ballantyne.  No  hint 
of  such  a  necessity  is  to  be  found  in  the  Specification,  and  I  think  the 
hypothetical  chemist  was  entitled  to  suppose  that  the  process  de- 
scribed in  the  Specification  was  sufficient  to  effect  its  purpose,  and, 
having  applied  that  process  and  failed  to  produce  the  result,  was 
entitled  to  consider  himself  misinformed,  without  resorting  to  exper- 
iment to  see  in  what  manner  the  directions  failed.  The  discovery 
was  entirely  new  and  contrary  to  anticipation,  and  the  process  de- 
scribed by  Normann,  for  all  that  was  generally  known  on  the  subject, 
might  very  well  have  been  sufficient.  •  There  was  no  reason  to  pre- 
sume any  necessity  to  add  to  the  directions,  which  he  gave,  anything 
from  the  stock  of  common  knowledge.  What  appears  to  me  very 
strong  confirmation  of  the  insufficiency  of  the  Specification  is  to  be 
found  in  the  evidence  of  Dr.  Lewkowitsch,  a  great  authority  on  the 
subject.  Dr.  Lewkowitsch  had  endeavoured  himself  to  obtain  the 
saturation  of  oleic  acid  by  the  use  of  nickel  as  a  catalyst  and  had 
failed.  He  afterwards  became  acquainted  with  Normann's  Specifica- 
tion, and  tried  a  further  series  of  experiments  with  no  greater  success. 
He  had  obtained  his  catalyst  from  a  solution  of  sulphate  of  nickel. 


APPENDIX  027 

He  afterwards  read  some  further  Papers  by  Sabatier,  published  in 
1905,  recommending  amongst  other  things  the  use  of  nitrate  in  place 
of  sulphate  of  nickel,  and  pointing  out  that  nickel  lost  its  catalytic 
properties  if  exposed  to  too  high  a  temperature.  With  these  hints, 
Dr.  Lewkowitsch  recommenced  his  experiments,  and  after  several 
years  succeeded  in  solving  the  problem.  It  is  said  for  the  Plaintiffs, 
and  truly  said,  that  sulphur  was  known  to  be  what  is  called  a  poison 
to  a  catalyst  and  that  therefore  sulphate  of  nickel  ought  not  to  have 
been  employed,  but  the  precipitate  was  properly  washed,  and  there 
was,  in  1903,  no  reason  to  suppose,  if  this  was  done,  that  sulphur 
to  an  injurious  extent  would  remain.  Moreover,  no  warning  is  given 
in  Normann's  Specification  against  the  use  of  sulphate  of  nickel,  or 
as  to  the  temperature  to  be  employed  in  reduction.  The  evidence 
in  this  case  shows  that  a  catalyst  prepared  from  the  sulphate  may 
be  successful,  and  also  that  nickel  may  be  heated  to  a  red  heat  with- 
out destroying  its  catalytic  properties.  Certain  passages  in  subse- 
quent publications  of  Dr.  Lewkowitsch  have  been  referred  to  as  dis- 
counting the  evidence  given  by  him  in  this  action.  It  seems  to  me 
that  they  do  not  diminish  the  weight  of  his  testimony.  Here  was  a 
chemist,  having  special  acquaintance  with  the  subject,  who  tried  a 
method  of  saturating  oleic  acid,  identical  with  that  described  by  Nor- 
mann,  and  failed,  studied  Normann's  Specification  and,  after  repeated 
experiments,  again  failed,  and,  after  receiving  what  he  says  was  a 
clue  from  a  publication  by  Sabatier  in  1905,  succeeds  only  then  after 
experiments  extending  over  several  years.  So  that  we  find  a  chemist 
of  exceptional  qualifications,  deeply  interested  in  the  subject,  failing 
for  years,  after  repeated  experiments,  and  careful  study  of  Normann's 
Specification,  to  achieve  what  I  am  asked  to  believe  any  competent 
chemist  could,  in  1903,  have  achieved  by  following  Normann's  direc- 
tions, without  any  experiment  at  all. 

In  this  connection  I  cannot  but  remind  myself  that,  though  the 
Patent  was  taken  out  in  1903  and  purported  to  reveal  a  process  of 
immense  commercial  value,  no  evidence  has  been  called  to  show  that 
anyone  succeeded  in  taking  advantage  of  the  discovery  for  a  consider- 
able number  of  years  after  its  publication;  that  the  only  evidence  of 
sufficiency  is  the  evidence  of  eminent  chemists  who  essay  to  prove  by 
experiments  in  1912  that  the  directions  contained  in  the  Specification 
were  in  1903  sufficient  to  ensure  success. 

I  come  to  the  conclusion  that  the  directions  in  Normann's  Specifi- 
cation were  insufficient;  and  I  infer,  both  from  the  evidence  before  me, 
and  the  lack  of  evidence,  that,  great  as  the  discovery  that  unsaturated 
fatty  acids  and  their  glycerides  could  be  hydrogenated  by  the  catalytic 


628  APPENDIX 

method  undoubtedly  was,  no  practical  means  of  taking  advantage  of 
the  discovery  were  disclosed  until  after  further  experiment  subsequent 
to  the  date  of  the  Patent. 

It  has  been  repeatedly  urged  that,  catalysis  depending  upon  contact, 
the  difference  between  success  or  failure  is  simply  a  question  of  obtain- 
ing or  failing  to  obtain  contact.  In  my  opinion,  the  evidence  fails  to 
establish  this  in  any  material  sense.  There  is  nothing  to  show  that 
the  directions  of  Normann  do  not  suffice  to  get  contact.  Catalysis 
remains  a  mystery  to-day,  and  in  1903  nothing  whatever  was  known 
as  to  the  means  necessary  to  obtain  successful  contact  in  the  catalytic 
hydrogenation  of  oleic  acid,  or  any  other  fatty  acid  or  glyceride,  except 
what  was  disclosed  by  Normann  himself.  According  to  Mr.  Ballan- 
tyne's  evidence,  a  catalyst  which  succeeded  in  getting  "  contact  "  in 
this  sense  with  acetylene  after  Sabatier,  failed  with  Normann's  process. 
To  say  that  a  direction  to  pass  a  strong  current  of  hydrogen  through  a 
mixture  of  fine  nickel  powder  and  oleic  acid,  in  order  to  expose  the  acid 
to  the  action  of  hydrogen  and  the  catalytic  substance,  connotes  the 
resort  to  every  device  known  to  science  for  making  the  exposure  as 
complete  or  as  frequent  as  possible,  seems  to  me  extravagant. 

I  therefore  come  to  a  conclusion  adverse  to  the  Plaintiffs'  contention 
upon  their  own  case;  but  I  do  not  concur  in  the  construction  of  the 
Specification  put  forward  on  their  behalf.  It  has  been  contended  that 
this  is  a  Patent  for  a  principle,  and  that  if  the  Patentee  shows  one  way 
of  carrying  it  out  he  is  entitled  to  claim  for  all  ways.  If  Normann  had 
invented  the  hydrogenation  of  oleic  acid  by  help  of  a  nickel  catalyst, 
and  had  given  sufficient  information  in  the  instance  stated  to  ensure 
success,  then  I  think  he  could  rightly  claim  all  other  ways  of  arriving 
at  the  result;  but  here  he  claims  to  have  invented  a  method  of  obtain- 
ing hydrogenation  of  all  unsaturated  fatty  acids  and  their  glycerides, 
and  if  his  method  fails  in  any  one  case  I  think  his  Patent  would  be  bad. 
Moreover,  he  claims  to  be  able  to  secure  the  result  by  the  use  of  finely- 
divided  platinum,  iron,  cobalt  and  copper  as  well  as  nickel,  and  if  the 
use  of  any  one  of  these  catalysts  is  fatal  to  his  process  I  think  his  Patent 
is  bad. 

There  are  other  matters  arising  in  the  action  which,  having  regard 
to  the  view  already  expressed,  are  not  necessary  for  the  decision  of  the 
case;  bub  1  may  say  that  I  think  that  the  evidence  shows  that  the 
temperature  at  which  hydrogenation  is  attempted  is  material,  not  only 
with  regard  to  time  occupied  in  obtaining  the  desired  reaction,  but  for 
obtaining  such  reaction  at  all.  It  may  be  that  one  element  of  success 
is  the  mixture  of  oxide  of  nickel  with  the  metal.  Dr.  Liebmann's 
experiments,  were  with  reduction  at  a  low  temperature,  300°  to  320° 


APPENDIX  629 

for  a  short  period,  one  hour,  while  Mr.  Hehner  in  the  experiments 
referred  to  reduced  at  360°  for  three  hours.  I  think  the  evidence 
shows  that  the  temperature  and  time  employed  by  Dr.  Liebmann  can- 
not be  relied  upon  to  obtain  complete  reduction.  It  will  be  observed 
that  both  Dr.  Liebmann  and  Dr.  Passmore,  when  seeking  to  demonstrate 
that  catalysts  prepared  in  a  manner  similar  to  that  adopted  by  the 
Defendants'  witnesses  could  be  used,  not  only  in  all  cases  resorted  to 
stirring,  but  used  a  much  larger  current  of  hydrogen  than  that  used 
in  previous  experiments.  Having  heard  the  evidence  upon  the  point, 
I  will  add  that,  could  Normann's  Patent  have  stood,  in  my  judgment, 
the  Defendants  would  have  infringed  it. 

In  the  result,  I  am  of  opinion  that  the  Plaintiffs'  action  fails  and 
must  be  dismissed  with  costs.* 

As  the  statement  has  repeatedly  been  made  that  the  British  patent  to  Normann, 
for  hardening  fats,  had  been  declared  void  because  it  claimed  a  process  which  had 
become  public  property,  the  Oelwerke  Germania  *  have  taken  occasion  to  contradict 
this  assertion,  claiming  that  the  British  court  held  the  patent  void  solely  because  of 
an  insufficient  description  of  the  process;  thus  merely  on  account  of  a  purely  formal 
defect  in  a  peculiar  requirement  of  the  British  patent  law.  This  concern  observes 
that  there  are  no  requirements  in  the  German  patent  law  such  as  contained  in  the 
British  patent  law,  and,  that  in  no  wise  did  the  British  court  hold  the  process  to  be 
public  property;  on  the  contrary,  it  stated  emphatically  that  if  this  defect  in  the 
specification  had  not  been  present,  judgment  would  have  been  given  against  the 
defendant  for  infringement  of  the  patent.  The  formal  defect  at  fault  has,  in  the 
meantime,  been  removed  by  a  process  peculiar  to  the  British  law.  The  further 
statement  is  made  that  the  British  statute  places  more  extensive  requirements  on  the 
patent  specifications  than  does  the  German  statute,  even  in  such  matters  as  are 
incidental  to  the  specific  nature  of  the  invention  concerned.  In  case  of  insufficient 
observance  of  these  requirements  on  the  part  of  the  applicant  for  patent,  the  patent 
may  subsequently  be  invalidated  on  motion;  on  the  other  hand,  a  patent  thus 
declared  void  may  be  re-established  by  removing  the  defect  in  the  specification  or 
by  supplementing  the  specification. 

*  Seifen.  Ztg.,  1914,  1260. 


APPENDIX  B 


EDIBLE  HYDROGENATED  FATS.      PATENT    LITIGATION. 

KREAM-KRISP 


CRISCO    AND 


Litigation  between  the  Procter  &  Gamble  Company  and  the 
Berlin  Mills  Company  involving  the  status  of  a  patent  owned  by 
the  former  concern  has  brought  forth  many  matters  of  general  or  his- 
torical interest  in  the  field  of  oil  hardening  and  the  endeavor  has 
been  made  to  include  here  extracts  from  the  briefs  of  the  opposing 
parties,  sufficient  in  extent  to  embrace  what  appear  to  be  the  more 
important  data  and  discussion.  Lack  of  space  forbids  the  publica- 
tion of  the  record  in  full  and  for  complete  details  the  reader  is 
referred  to  the  Court  records.* 

The  author  is  indebted  to  Mr.  Alfred  M.  Allen  f  for  a  copy  of 
the  brief  for  plaintiff  and  to  Mr.  John  C.  Pennie  J  for  a  copy  of 
defendant's  record,  for  which  thanks  are  gratefully  acknowledged. 

UNITED  STATES  DISTRICT  COURT, 

SOUTHERN  DISTRICT  OF  NEW  YORK. 


THE  PROCTER  &  GAMBLE  COMPANY, 
Plaintiff, 
vs. 

BERLIN  MILLS  COMPANY, 

Defendant. 


In  Equity. 
No.  13-100. 


BRIEF  FOR  PLAINTIFF. 
Before  JUDGE  AUGUSTUS  N.  HAND. 


KERR,  PAGE,  COOPER  &  HAYWARD, 

Solicitors  for  Plaintiff. 
LIVINGSTON  GIFFORD, 
ALFRED  M.  ALLEN, 
THOMAS  B.  KERR, 

Of  Counsel 

*  Citations  to  court  decisions  and  the  record  have  been  largely  omitted, 
t  Of  firm  of  Allen  &  Allen,  Cincinnati,  Ohio. 

J  Of  firm  of  Pennie,  Davis,  Marvin  &  Edmonds,  New  York  City. 

630 


EDIBLE  HYDROGENATED  FATS  631 

This  suit  is  for  infringement  of  patent  No.  1,135,351,  granted  to  the  plaintiff 
as  assignee  of  John  J.  Burchenal  on  April  13th,  1915,  for  a  Food  Product.  The 
bill  was  filed  on  December  16th,  1915,  the  answer  filed  on  January  14th,  1916, 
and  an  amendment  to  the  answer  was  filed  on  September  22d,  1916.  The  an- 
swer set  up  a  large  number  of  prior  publications  and  patents  to  show  anticipa- 
tion and  the  prior  state  of  the  art  bearing  on  the  subject.  Bill  of  particulars 
were  granted  both  parties  and  the  issues  narrowed  to  a  certain  definite  number 
of  prior  patents  and  publications  and  to  the  first  and  second  claims  of  the  patent 
in  suit.  Prior  to  the  trial  the  defendant  took  a  large  number  of  depositions 
de  bene  esse  which  have  been  printed  for  the  use  of  the  court  in  a  book  of  410 
pages  entitled  '"  Defendant's  Exhibit,  Depositions  de  bene  esse,"  which  deposi- 
tions were  offered  and  admitted  in  evidence  at  the  time  of  the  trial.  The  trial 
began  on  March  21st  and  was  completed  March  29th,  at  which  time  the  argu- 
ment and  filing  of  briefs  was  set  for  April  28th. 

The  defenses  set  up  were  anticipation,  prior  invention  by  one  Kayser,  lack 
of  invention,  limitations  by  Patent  Office  proceedings,  insufficiency  of  specifi- 
cation and  non-infringement. 

*  *     * 

THE  PATENT  IN  SUIT 
In  making  the  product,  the  patent  says: 

In  manufacturing  this  product  cottonseed  oil  or  other  vegetable  oil  is 
caused  to  chemically  absorb  a  limited  amount  of  hydrogen  by  reacting 
on  the  oil  with  hydrogen  in  the  presence  of  a  catalyzing  agent  and  at 
an  elevated  temperature. 

*  *     * 

The  only  claims  in  issue  are  claims  1  and  2,  which  are  as  follows: 

1.  A  homogeneous  lard-like  food  product  consisting  of  an  incompletely 
hydrogenized  vegetable  oil. 

2.  A    homogeneous    lard-like   food    product    consisting   of   incompletely 
hydrogenized   cottonseed  oil. 

*  *     * 

The  great  benefit  of  the  invention  is  not  mentioned  in  the  patent,  but  really 
constitutes  the  basis  for  an  award  in  favor  of  the  patentee,  namely,  that  it  was 
the  creation  of  a  new  class  of  food  products  of  superior  quality,  free  from  the 
objections  existing  against  animal  products,  and  was  the  foundation  of  a  now 
great  industry  known  as  the  Hydrogenated  Food  Product  Industry,  which  has 
conferred  an  enormous  benefit  upon  the  public  and  entitled  the  inventor  to  be 
enrolled  high  in  the  ranks  of  its  benefactors. 

*  *     * 

In  both  the  processes  of  manufacturing  Crisco  and  Kream-Krisp  "  the 
amount  of  hydrogen  absorbed  is  carefully  regulated  and  limited "  by 
the  operator,  so  that  Crisco  is  given  a  melting  point  of  34  to  36  C.,  and 
the  sample  of  Kream-Krisp  in  evidence  was  given  a  melting  point  of 
35.7;  the  melting  point  given  in  the  patent  being  from  33  to  40.  By 
stopping  the  hydrogenizing  when  the  melting  point  has  reached  any  of 
these  degrees,  or  even  a  degree  slightly  in  excess,  the  "  product  which 


632  APPENDIX 

cools  to  a  white  or  yellowish  semi-solid  "  is  obtained,  which  is  specified 
in  claims  1  and  2. 

It  is  thus  seen  that  the  gist  of  the  novelty  of  the  process,  namely,  that 
"  the  operation  is  stopped  when  the  oil  has  been  converted  into  a  product 
which  cools  to  a  white  or  yellowish  semi-solid  "  is  followed  by  defendant 
in  making  Kream-Krisp,  the  same  as  by  the  plaintiff  in  making  Crisco, 
and  that  the  melting-point  test  by  which  defendant  secured  this  semi- 
solid  result  was,  in  the  case  of  the  Kream-Krisp  in  evidence,  with  the 
range  of  Crisco  melting  point,  and  also  the  patent  in  suit  melting  point. 

Since  all  three  melting  points  are  within  the  same  narrow  range  from 
33  to  40,  it  is  inevitable  that  all  three  are  semi-solid,  or  lard-like,  at 
ordinary  temperature,  and  the  evidence  shows  conclusively,  that  that  is 
what  the  average  cook  wants. 

Moreover,  by  an  inspection  of  the  specimens  of  Crisco  and  Kream- 
Krisp  in  evidence  the  court  can  see  for  itself  that  they  are  lard-like. 
Certainly  no  expert  is  needed  for  that. 


In  the  infringing  manufacture  defendant  uses  the  thermometer  only  to  keep 
its  product  at  the  desired  semi-solid  or  lard-like   consistency.     By  the  aid  of 
the  thermometer   the   hydrogenizing   is    "  carefully   regulated   and   limited."     If, 
therefore,  no  test  but  the  thermometer  is  used  in  carrying  on  the 
infringement,  why  should  any  other  test  be  applied    by  the  court 
in  deciding    the    question    of    infringement?      And,  if   any  chart  is 
desired,  why  should  any  chart  be  used  more  than  the  thermometer 
Efja       scale? 

"°™  On  this  page  we  have  produced  a  Centigrade  thermometer  scale 

from  zero  up  to  70  degrees,  and  noted  thereon  the  melting  points 
of  various  products. 

It  will  be  seen  that  on  this  scale  the  hard  approximately  saturated 
cotton-seed  oils  (60°)  and  Paal  &  Roth  (59°-60°)  range  themselves 
at  one  end  and  liquid  cottonseed  oil  stands  at  the  other  end,  while 
approximately  midway  range  the  semi-solid  or  lard-like  in  a  bunch, 
between  33  and  40  degrees.  Of  course  a  slight  variation  of  a  degree 
or  two  above  40  would  make  no  substantial  difference. 


It  appears  from  the  testimony  that  Burchenal  was  the  first  one  in 
whose   mind   the  thought  ever  arose  to  associate  a  hydrogenized 
body  with  food.      He  was  the  first  one  that  ever  even  asked  the 
question  whether  it  might  be  a  food,  and  he  was  answered  by  Kayser 
\/  in  the  negative.     He  was  the  one  that  followed  up  that  question 

by  the  experiments  necessary  to  determine  the  answer  in  the 
affirmative;  and  having  embodied  that  answer  in  a  successful  food  compound, 
he  was  the  first  to  make  the  additional  conception  and  discovery  of  the  possi- 
bility that  it  might  be  a  successful  food  product  in  still  a  second  form,  to  wit, 
the  partially  hydrogenized  form.  He  it  was  that  made  the  necessary  experi- 
ments to  answer  the  question  whether  this  idea  was  possible  or  not;  and  the 
generic  conception  had  been  made  and  worked  out  in  the  form  of  the  com- 
pound in  the  spring  of  1908,  a  year  and  a  half  before  the  specific  conception 


EDIBLE  HYDROGENATED  FATS  633 

was  made  or  worked  out  in  the  fall  of  1909  in  the  form  of  the  partially  hydro- 

genized  product,  which  is  the  subject  of  claims  1  and  2  in  suit. 

Burchenal's  conception  had  its  rise  under  the  following  circumstances: 

Soap  makers  in  England,  the  Crossfields  in  particular,  had  introduced  hydro- 

genized  cotton  seed  oil  into  the  soap  making  industry. 

The  plaintiff  was  engaged  in  the  manufacture  of  soap  in  this  country,  and  in 

the  fall  of  1907  it  received  a  letter  from  E.  C.  Kayser,  dated  Cheshire,  England, 

October  18th,  1917,  as  follows: 

"  Dear  Sirs: 

"  In  a  few  weeks'  time  I  shall  be  en  route  to  the  States,  when  I  pro- 
pose introducing  a  new  process  of  the  greatest  possible  importance  to  soap 
manufacturers. 

"  I  have  manipulated  this  process  for  the  last  three  years  and  am  the 
only  person  thoroughly  acquainted  therewith. 

"  Kindly  inform  me  by  the  earliest  mail  if  you  wish  me  to  call  upon 
you  in  the  first  instance  and  if  in  that  case  you  are  agreeable  to  refund 
railway  fares  from  New  York  or  other  port  to  your  city. 

"  Yours  faithfully, 

"E.  C.  KAYSER." 

In  response  to  this  letter  plaintiff  wrote  under  date  of  October  28th,  1907, 
inviting  Kayser  to  come  to  Cincinnati,  Def.  Dep.,  p.  208,  bringing  with  him 
samples  of  hydrogenated  material  being  used  by  the  Crossfields  in  making  soap. 

These  samples  were  shown  by  Kayser  to  Burchenal,  who  describes  them  "  hard 
almost  white  in  appearance,"  Def.  Dep.,  Ans.  40,  "  a  very  hard  material,  had  a 
very  high  melting  point,  had  an  unpleasant  taste"  Def.  Rep.,  Ans.  276;  "very 
hard,  a  good  deal  the  appearance  of  a  piece  of  porcelain  or  china." 

Procter  &  Gamble  made  a  preliminary  agreement  with  Kayser,  dated  Decem- 
ber 5,  1907,  to  make  what  the  agreement  referred  to  as  "  hardened  "  material. 
Thereupon  they  erected  an  apparatus  for  Kayser  and  he  proceeded  with  his 
experiments.  His  sole  effort  was  to  make  a  substantially  saturated  material. 
Burchenal  testified: 

"  The  sole  effort  was  toward  making  a  saturated  material.  That  was 
indicated  by  its  Wdness "  Def.  Dep.,  Ans.  158.  "  The  effort  was  to 
make  a  saturated  material  and  wherever  we  didn't  get  that,  we  didn't 
look  upon  it  as  a  successful  operation,"  Def.  Dep.,  Ans.  162.  "  Hard 
material — that  was  where  our  effort  was  at  that  time."  Def.  Dep.,  Ans. 
164.  "  There  was  really  no  object  and  no  sense  in  taking  them  "  (sam- 
ples to  ascertain  the  progress  of  the  operation.)  "  We  were  trying  to 
saturate  the  material  and  that  was  indicated  by  the  absorption  of  hydro- 
gen. I  can't  say  we  did  not  take  samples,  but  in  the  ordinary  conduct 
of  things  there  was  no  occasion  to  take  samples." 

Kayser's  report  of  January,  '08,  said: 

"  Completion  of  saturation  is  indicated  by  comparison  of  volume  of  gas 
in  and  out  of  machine.  When  saturation  is  practically  complete,  the  gas 
passes  through  without  any  apparent  reduction  in  volume." 

The  hydrogenized  oil  cannot  be  used  as  soap  without  chemical  change.     It  is 


634  APPENDIX 

treated  chemically  with  an  alkali,  such  as  potash  or  soda,  or  saponified,  and  it 
is  this  saponification  of  the  hydrogenized  body  which  is  soap. 

The  first  time  that  anybody  seems  to  have  associated  any  hydrogenized  body 
with  food  was  when  Burchenal  asked  Kayser  the  question  in  October  or  Novem- 
ber, 1907: 

"  I  asked  him  if  he  thought  it  would  do  for  edibles,  and  he  said  he 
thought  not." 

It  is  not  difficult  to  realize  why  it  had  never  been  associated  with  the  food 
art  before,  because  as  pointed  out  by  Burchenal,  "  it  did  not  appear  to  be 
edible;  it  was  a  very  hard  material,  had  a  very  high  melting  point,  had  an  un- 
pleasant taste." 

McCaw  in  reference  'to  a  sample  of  this  Kayser  material  submitted  to  him  by 
Mr.  Procter,  says: 

I  immediately  tasted  it,  examined  its  texture,  and  he  asked  me  if  I 
thought  a  lard  substitute  could  be  made  from  it,  that  is,  if  it  would 
take  the  place  of  oleo  stearin.  I  replied  that  it  would  not,  giving  as  my 
reasons  that  the  flavor,  structure  and  material,  and  its  hardness,  were  all 
unfit  for  that  purpose. 

It  should  be  remembered  too  that  it  was  already  associated  with  the  soap 
making  art  by  the  Crossfields,  and  that  to  be  used  as  soap  it  first  had  to  be 
chemically  changed  or  saponified;  all  of  which  was  antagonistic  to  any  idea 
of  its  being  used  without  saponification,  and  particularly  for  food.  Moreover 
to  any  one  familiar  with  the  complexities  of  cotton  seed  oil  and  its  hydro- 
genization,  the  presumption  was  that  it  would  contain  ingredients  entirely  incom- 
patible with  food  requirements,  and  possibly  even  poisonous. 

Following  his  own  idea,  which  does  not  seem  to  have  been  shared  by  any  one 
else,  that  it  might  constitute  a  food,  Burchenal  followed  the  matter  up.  He  says: 

"  As  soon  as  I  saw  the  material  that  he  (Kayser)  brought  there,  I  made 
up  my  mind  that  I  would  endeavor  to  ascertain  if  it  was  edible.  I  went 
into  the  thing,  I  examined  the  material;  we  worked  on  that." 

Burchenal  also  proceeded  to  mix  the  hard,  hydrogenized  product  with  cotton 
seed  oil  so  as  to  reduce  it  from  its  inedible  hardness  down  to  an  edible  semi- 
hardness.  He  had  considerable  difficulty  in  doing  this,  and  sent  the  hardened 
material  down  to  the  McCaw  Company  in  Macon,  Georgia,  about  May,  1908, 
because  of  their  having  proper  machinery  for  mixing.  At  that  time  the  idea  of 
the  availability  of  a  partially  hydrogenized  substance  had  not  entered  his  mind. 
The  sole  idea  up  to  that  time  was  to  completely  hydrogenize  and  then  reduce 
the  hardness  by  mixing  with  cotton  seed  oil,  and  Burchenal  appears  to  have 
entertained  this  idea  as  the  sole  means  of  attaining  a  food  product  until  about 
a  year  and  a  half  after  he  had  had  his  first  mixture  made,  or  until  the  autumn 
of  1909.  Burchenal  testifies: 

Well,  how  long  after  that  (after  spring  of  1908)  was  it  that  you  first 
produced  a  food  product  consisting  of  an  incompletely  hydrogenized  vege- 
table oil?  A.  Well,  I  think  our  first  report  on  that  is  some  time  in  1909. 
I  would  like  to  qualify  that,  however,  so  as  to  show  that  that  material 
was  not  produced  in  a  commercial  way  at  that  time,  and  was  experimental. 


EDIBLE   HYDROGENATED  FATS  635 

Mr.  Burchenal  says: 

I  think  I  am  safe  in  saying  that  the  date  on  which  that  material  was 
first  produced  in  any  appreciable  quantities,  was  after  April  26,  1910, 
and  in  all  probability  prior  to  July  1,  1910.  *  *  *  In  an  experimental  way, 
I  should  say  about  October  or  November,  1909. 

Morrison  (defendant's  de  bene  depositions,  p.  316,)  testifies: 

Q.  21.  When  did  you  first  have  the  semi-solid  hydrogenated  cotton- 
seed oils  sent  to  you  for  examination  as  to  their  physical  characteristics? 
A.  Some  time  in  1909  was  when  I  first  came  in  contact  with  it. 

Thus  we  have  brought  the  history  of  the  rise  and  progress  of  Burchenal's 
invention  from  the  conception  of  a  food  possibility,  through  the  various  stages, 
down  to  the  making  of  the  product  which  is  the  subject  of  claims  1  and  2  in 
suit,  covering  a  period  of  upwards  of  two  years  from  the  fall  of  1907  until  the 
fall  of  1909,  or  the  spring  of  1910.  It  was  first  put  on  the  market  in  April, 
1911.  Taylor,  Ans.  11  and  the  sales  thereafter  were  for  2,600,000  Ibs.;  1912,  14,- 
500,000;  1913,  23,800,900;  1914,  40,000,000;  1915,  47,700,000  and  1916,  60,500,000, 
or  about  190,000,000  Ibs.  At  the  price  ruling  in  1916,  this  would  make  a  value 
of  over  $34,000,000. 

The  various  stages  of  Burchenal's  progress  may  be  summarized  as  follows: 

1.  Fall  of  1907.     Conceived  possibility  that  the  hydrogenated  substance  might 
be  utilized  in  the  food  product  art,   notwithstanding  its  intrinsic  evidences  to 
the  contrary. 

2.  Winter  of  1907-8.     Discovered  the  correctness  of  his  conception  by  inves- 
tigation of  the  hard,  hydrogenized  product. 

3.  Spring   of    1908.     Invented   a   household   form   embodying   said   conception 
and  discovery  (i.e.,  the  mixture  or  compound  which  is  the  subject  of  his  patent 
1,135,935). 

4.  From  spring  of  1908  to  fall  of  1909.     Perfected  the  compound  and  intro- 
duced it  commercially  as  "  Flake  White." 

5.  Fall   of    1909.     Conceived   of   the   possibility   of   the   improved   form    (i.e., 
the  partially  hydrogenized  form  which  is  the  subject  of  claims  1  and  2  in  suit.) 

6.  Fall  of  1909.     Invented  Crisco  as  the  embodiment  of  said  last  conception. 

7.  1910  and  1911.     Perfected  Crisco  and  introduced  it  commercially. 

8.  1911    to    1916.     Sales    of    Crisco   amounted    to   over    189,200,000   pounds, 
representing  a  market  value  of  over  $34,000,000. 


It  is  well  to  pause  for  a  moment  to  consider  how  beneficent  are  these  house- 
hold products. 

From  the  physiological  standpoint  they  are  free  from  all  detrimental  ingre- 
dients or  properties.  Being  all  vegetable  they  are  so  free  from  the  suspicion 
of  microbes  of  animal  origin  that  they  are  immune  from  the  government  inspec- 
tion at  the  factory  of  animal  food  products.  Crisco  in  particular  is  free  from 
indigestible  components. 

From  the  household  standpoint  Crisco  requires  a  minimum  of  skill  or  exertion 
to  distribute  it  throughout  the  dough,  and  it  remains  so  distributed  throughout 
the  cooking  operation.  It  is  less  susceptible  to  oxidation  and  consequent  ran- 


636  APPENDIX 

cidity  than  the  liquid  oil.  It  is  less  susceptible  to  smoking  or  burning  because 
it  can  be  heated  to  a  higher  temperature  without  doing  so.  Being  lard-like, 
the  ordinary  cooking  recipes  requiring  lard  are  satisfied  by  it,  and  it  can  be 
scooped  out  of  its  container  and  measured  conveniently  and  accurately  as  is  lard. 
Added  to  all  the  above  advantages  is  the  fact  that  the  introduction  by  Bur- 
chenal  of  hydrogenized  substances  into  the  food  product  art  has  enormously 
enlarged  the  resources  of  that  art  and  prevented  the  lard-like  food  products  from 
mounting  to  prices  even  higher  than  those  current  at  the  present  time. 

*    *    * 

Up  to  the  time  of  Burchenal's  inventions  such  a  thing  as  a  hydrogenized  food 
industry,  or  a  hydrogenized  food  of  any  kind  had  absolutely  no  existence.  It  is 
to  Burchenal,  and  Burchenal  alone,  that  Procter  &  Gamble  owed  the  knowledge 
enabling  them  to  introduce  and  establish  the  hydrogenized  food  industry.  The 
success  of  that  industry  is  startling,  and  the  benefit  to  mankind  in  the  enlarge- 
ment of  food  products  is  unbounded.  The  various  witnesses  in  this  case  coming 
from  the  other  concerns  in  this  industry,  such  as  Swift  &  Co.  and  this  defendant, 
and  the  Ward  Company,  had  to  acknowledge  that  they  knew  of  no  industry 
of  this  kind  anterior  to  its  being  established  by  Procter  &  Gamble  under  the 
Burchenal  inventions. 

NOVELTY 

The  prior  art  consisted  of  cotton  seed  oil  (1)  liquid,  (2)  solid  or  hard. 

The  liquid  cotton  seed  oil  had  a  melting  point  of  about  zero  C.,  and  the  only 
melting  point  for  the  solid  hard  cotton  seed  oil  given  in  the  prior  patents  and 
publications  was  the  56  to  60  C.  given  by  Paal  &  Roth  in  the  Berichte  of  1909, 
Vol.  42.  They  described  it  in  two  ways,  as  follows:  "  A  yellowish  white,  brittle 
mass  which  melted  at  56°  to  60°."  "  Brittle  mass,  nearly  white  in  color,  which 
melted  at  57°  to  60°." 

Semi-solid  or  lard-like  cotton  seed  oil  was  new. 

Defendant  contends  that  in  the  progressive  hydrogenizing  from  the  liquid 
to  the  solid,  the  oil  passed  through  the  semi-solid  state,  and  that  some  of  the 
samples  taken  for  testing  would  have  been  semi-solid.  This  fact  is  immaterial 
in  the  eye  of  the  patent  law  under  the  following  propositions: 

1.  An  incidental  production  while  in  pursuit  of  another  object,  and  not  excit- 
ing attention,  or  supposed  to  possess  any  value,  does  not  constitute  an  anticipa- 
tion. 

2.  A  production  not  in  the  food  product  art  cannot  anticipate. 

3.  A  production,  the  qualities  of  which  were  not  recognized  for  the  purpose 
of  the  patent,  does  not  anticipate. 

4.  A  change,  however  slight,  which   capacitates    a    new  result,  differentiates 
from  an  anticipation. 

The  samples  taken  in  the  course  of  the  prior  production  of  the  hard  solid 
substance,  if  any,  were  in  minute  quantities  in  the  crude  state,  and  were  thrown 
away  as  soon  as  tested.  Not  being  intended  for  a  food  product  they  were  not 
filtered  to  remove  the  catalyst,  nor  deodorized,  nor  chilled. 

It  appears  that  the  only  industrial  use  made  of  the  knowledge  contained 
in  the  prior  art  patents  and  publications  was  in  soap  making.  Burchenal  tes- 
tifies that  when  he  visited  the  Crossfields  in  Europe  they  were  using  it  for  soap 
making  (Ans.  319),  and  when  Kayser  came  to  this  country  from  Europe  the  only 


EDIBLE  HYDROGENATED  FATS  637 

use  he  reported  was  for  soap  making  (Ans.  267  and  318).  Notwithstanding  the 
fact  that  the  Normann  patent  was  in  1903,  and  that  therefore  the  hydrogenizing 
of  oil  had  existed  for  years,  there  does  not  appear  to  have  been  even  a  sus- 
picion either  in  the  patents  or  publications,  or  in  industrial  use  of  its  having 
any  application  to  the  art  of  food  products  whatsoever  prior  to  Burchenal's 
conception. 

The  prior  patents  and  publications  are  all  in  the  same  category.  Their  sole 
aim  was  to  produce  saturation.  This  appears  on  their  face. 

*    *    * 

It  must  be  perfectly  manifest  to  the  court  that  the  idea  that  a  semi-solid, 
produced  by  stopping  the  hydrogenizing  at  that  point,  would  have  utility,  never 
entered  the  mind  of  any  one  until  Burchenal,  much  less  that  it  or  any  other 
degree  of  hydrogenizing  would  have  any  application  in  the  food  product  art. 

Not  only  this,  but  Dr.  Baskerville  also  points  out  that  the  knowledge  of  the 
process  of  hydrogenation  as  it  existed  prior  to  the  date  of  the  Burchenal  inven- 
tion would  have  tended  to  repel  the  idea  that  the  product  might  be  edible.  He 
says  in  answer  to  Q.  186,  Rec.,  page  752,  as  follows: 

In  the  Normann  British  patent  No.  1,515,  of  1903,  there  appears  on 
Page  2  of  the  typewritten  copy  submitted  the  following: 

"  Apart  from  the  formation  of  small  quantities  of  nickel  soap,  which 
may  be  easily  decomposed  by  dilute  mineral  acids." 

That  indicates  that  the  product  contained  something  which  is  not 
regarded  as  suitable  for  food  and  would  require  special  treatment  for  the 
removal  of  nickel  soaps,  a  treatment  with  an  acid. 

In  the  communication  of  Paal  &  Roth,  from  the  article  occurring  in 
Berichte  der  Deutschen  Chemischen  Gesellschaft,  Volume  42,  beginning 
at  Page  1541,  of  1909,  there  occurs  on  Page  1  of  the  translation  submitted 
the  following: 

"  The  hydrogenation  of  the  esters  of  the  unsaturated  fatty  acids, 
whereby  esters  of  saturated  fatty  acids  were  produced,  led  to  a  deep- 
seated  change  in  the  properties  of  the  fats,  the  new  products  being  pul- 
verizable,  crystalline  masses." 

On  the  same  page,  at  the  bottom,  and  at  the  top  of  Page  2,  appears 
the  following: 

"  In  accomplishing  this,  the  remarkable  fact  was  established  that  not 
only  were  the  glycerine  esters  of  unsaturated  acids  hydrogenated  but  also 
certain  other  non-fatty,  saponifiable,  companion  substances  which  are 
present  to  a  slight  extent  in  the  original  fats. 

"  In  our  last  communication  we  stated  that  the  reduced  cod  liver  oil, 
with  its  iodin  number  3,  no  longer  showed  the  characteristic  color  reaction 
of  this  oil  which  depends  on  the  presence  of  lipochromes.  Similarly, 
observations  were  made  with  sesame  and  with  cottonseed  oil." 

Further  down  the  page  appears  the  following: 

"  Similarly,  the  very  poisonous  croton-oil  was  converted  by  hydro- 
genation into  a  perfectly  non-poisonous  tallow." 

On  page  3  in  the  same  article  there  appears  the  following: 

"  We  found  again,  as  mentioned  in  the  former  paper,  that  for  the  com- 
plete hydrogenation  of  all  the  fats  more  hydrogen  was  required  than  was 


638  APPENDIX 

theoretically  necessary,  as  indicated  by  the  iodin  number  of  the  original 
fat.  In  some  cases  this  excess  consumption  of  hydrogen  was  very  con- 
siderable. Moreover,  we  could  repeatedly  confirm  the  fact  that  although 
more  hydrogen  had  been  taken  up  than  was  to  be  expected  from  the  orig- 
inal iodin  number,  so  that  one  would  not  have  expected  any  more  unsat- 
urated  acids  to  be  present,  still  the  hydrogenated  fat  showed  an  iodin 
number,  very  small  to  be  sure  in  some  cases. 

"  Naturally  the  simplest  way  to  account  for  this  excess  consumption 
of  hydrogen  was  to  assume  leakage  from  the  apparatus.  This,  however, 
is  contradicted  by  the  fact  that  after  a  while  the  volume  of  hydrogen 
remained  constant  which  would  not  be  the  case  if  there  was  any  chance  of 
leakage.  For  this  reason,  the  only  way  to  account  for  the  excess  hydro- 
gen is  to  assume  that  some  other  reduction  took  place,  as,  for  example, 
the  reduction  of  glycerides  of  the  oxy-fatty  acids  or  a  reduction  cleavage 
of  the  glycerides  into  aldehyde  and  alcohol." 

On  Page  7  there  appears  the  following: 

"As  it  was  of  interest  to  study  the  phsyiological  action  of  both  the  par- 
tially and  completely  hydrogenated  oil,  two  other  reduction  experiments 
were  performed." 

In  this  connection  I  wish  to  state  that  one  would  have  been  in  the 
dark  and  would  not  have  known  what  might  be  present  in  partially  hydro- 
genized  material.  It  might  have  been  poisonous,  it  might  have  been 
harmless.  In  fact,  evidently  Paal  was  mindful  of  this,  because  he  took 
precautions  to  have  physiological  experiments  made.  This  is  indicated 
on  Page  13  of  this  article  of  the  translation: 

"  Cottonseed  oil  gives  the  Becchi  and  Halphen  tests  which  are  used 
in  food  chemistry  for  detecting  the  presence  of  this  oil  when  used  as  an 
adulterant.  The  cause  of  the  first  reaction  is  the  presence  of  a  small 
quantity  of  unsaponifiable  constituent  which  has  not  been  characterized 
further  chemically  except  that  it  is  capable  of  reducing  an  alcoholic- 
ethereal  solution  of  silver  nitrate  to  metallic  silver.  The  constituent  of 
cottonseed  oil  which  causes  the  Halphen  reaction  (red  coloration  on  heat- 
ing with  a  mixture  of  amyl  alcohol  and  sulphur  dissolved  in  carbon  disul- 
fide)  is  also  found  in  the  unsaponifiable  part  of  cottonseed  oil." 

On  page  14  there  appears  the  following: 

"  Both  the  hydrogenated  products  which  we  obtained  from  cotton-seed 
oil  failed  to  give  either  of  the  above  tests.  This  shows  that  the  unsaponi- 
ifiable  constituents  as  well  as  the  unsaturated  fatty  acids  are  acted  upon 
by  the  catalytic  reduction,  and  in  this  case  the  effect  was  permanent, 
for  negative  tests  were  obtained  even  after  the  products  had  stood  for 

ten  months." 

*    *     * 

INFRINGEMENT 

The  infringing  Kream-Krisp  is  represented  in  this  case  by  the  can  stipulated, 
with  its  labels  and  pamphlet  circulars. 

That  it  is  a  lard-like  food  product  appears  from  inspection,  and  is  clearly 
implied  by  its  label: 

Dr.  Baskerville  confirms  this  by  testifying  that  it  is  a  lard-like  food  product 
and  a  substitute  for  Crisco. 


EDIBLE  HYDROGENATED  FATS  639 

That  it  is  hotnoyerteous  is  clear  upon  inspection.  Dr.  Baskcrvillc  so  testifies, 
and  is  not  denied  in  the  record. 

That  it  was  made  from  cotton  seed  oil  by  the  addition  of  hydrogen  is  stip- 
ulatecj. 

That  its  hydrogenizing  is  incomplete  in  the  sense  of  the  patent  in  suit  appears 
from  its  semi-solid  consistency. 

*     *     * 

In  any  continuous  process  like  defendant's  Moore  process,  as  well  as  in  any 
batch  process,  the  three  factors  of  hydrogenizing,  the  oil,  hydrogen,  and  the 
catalyst,  are  brought  together,  and  both  defendant's  process  and  the  process 
described  in  the  Burchenal  patent  stop  the  hydrogenizing  at  the  semi-solid  range 
by  limiting  the  time  that  they  remain  in  contact.  Dr.  Walker  admitted  that 
this  was  done  in  defendant's  process  by  regulating  the  velocity  of  the  flow  of 
oil  through  the  catalyzer.  The  result  of  the  defendant's  operation  is  described 
by  Dr.  Walker  as  he  understands  it,  Ans.  125;  Rec.,  p.  526,  and  immediately 
in  the  next  answer  he  admits  that  in  the  batch  process  the  result  is  the  same, 
except  as  to  percentages.  If  any  cotton  seed  oil  and  hydrogen  get  through 
defendant's  catalyzer  without  being  catalyzed,  the  same  would  be  true  if  the 
batch  process  were  conducted  carelessly  with  insufficient  agitation. 

The  Moore  patent  shows  that  no  substantial  amount  of  hydrogen  and  oil 
gets  through  the  catalyst  without  being  catalyzed  when  the  apparatus  is  prop- 
erly constructed,  because  it  acknowledges  that  such  might  occur  if  the  dia- 
phragm were  cracked.  It  states  that  this  difficulty  has  been  overcome.  It 
says  (patent  No.  1,184,480,  p.  4,  line  45):  "One  of  the  difficulties  that  I  have 
met  with  practically  in  the  operation  of  an  apparatus  of  this  character  having  a 
diaphragm  of  large  area  has  been  due  to  the  occasional  cracking  of  the  catalytic 
layer,  and  also  due  to  the  expansion  of  the  casing  which  forms  cracks  or  spaces 
at  the  outer  edges  of  the  diaphragm,  through  all  of  which  cracks  and  spaces  the 
hydrogen  escapes  into  the  lower  compartment  thereby  permitting  some  of  the 
oil  to  pass  through  without  being  reduced,  and  so  reducing  the  pressure  above 
the  diaphragm  that  the  gas  will  pass  therethrough  in  only  limited  quantities. 
I  have  overcome  this  difficulty  by  incorporating  with  the  layer  of  catalytic 
material  long-fibered  asbestos^  as  hereinbefore  explained,  which  I  find  prevents 
the  formation  of  cracks.  The  difficulty  due  to  the  expansion  of  the  casing  has 
been  overcome  by  the  provision  of  the  ring  51  which  clamps  the  margins  of 
the  portions  of  the  diaphragm  against  the  outer  shell." 

Defendant's  evidence  shows  that  the  diaphragm  used  by  it  is  built  according 
to  this  improvement,  and  is  therefore  such  as  to  overcome,  as  the  Moore  patent 
says,  the  difficulty  of  "  permitting  some  of  the  oil  to  pass  through  without  being 
reduced."  This  accounts  for  the  fact  that  in  most  all  of  the  specimens  of 
Kream-Krisp  tested  by  plaintiff  there  was  no  unchanged  cotton  seed  oil  at 
all,  and  in  those  where  there  was  any  that  it  was  a  mere  trace,  such  as  about 
1  per  cent.  It  also  accounts  for  the  fact  that  in  defendant's  circulars  they  assert 
that  Kream-Krisp  contains  no  unchanged  oil. 

THE  HALPHEN  TEST 

The  patent  in  suit  describing  the  specific  product  claimed  in  claim  4,  says 
(p.  2,  line  7) :  "  it  shows  no  free  cottonseed  oil  when  subjected  to  the  Halphen 
test."  Defendant's  witness  Richter  testified  that  although  the  sample  of  Kream- 


640  APPENDIX 

Krisp  in  evidence  showed  no  response  to  this  test,  yet  all  other  samples  of 
defendant's  product  which  he  had  tested  did  respond  thereto.  Presumably  this 
testimony  was  intended  to  have  some  bearing  on  the  question  of  infringement. 
But  while  this  test  is  specified  in  Claim  4,  it  is  omitted  from  claims  1  and  2  in 
suit  and  is  therefore  irrelevant  to  the  present  issue. 

The  Halphen  test,  moreover,  is  irrelevant  and  immaterial  from  any  practical 
standpoint.  It  is  admitted  by  everybody  that  the  substance  which  reacts  in 
showing  the  test  is  so  minute  that  no  one  has  ever  determined  exactly  what  it  is. 
It  is  also  proved  by  Dr.  Baskerville,  Ans.  25,  Rec.,  p.  434,  and  Morrison,  Ans. 
53,  Rec.,  p.  781,  that  it  will  detect  the  presence  of  a  mere  trace  of  cotton  seed 
oil,  as  little  as  1  per  cent  or  less.  Therefore  the  fact  that  a  body  responds  to 
the  Halphen  test  does  not  show  that  it  contains  more  than  a  trace  of  cotton 
seed  oil,  such  as  could  not  possibly  make  any  practical  difference. 

Dr.  Baskerville  testifies,  Rec.  p.  747,  Ans.  160-164,  that  he  tested  three  dif- 
ferent specimens  of  Kream-Krisp  obtained  in  different  parts  of  the  country,  and 
that  none  of  them  responded  to  the  Halphen  test.  Morrison,  Rec.,  p.  781, 
Ans.  49-53,  testifies  that  he  had  tested  about  a  dozen  specimens  of  Kream- 
Krisp  and  that  the  majority  did  not  respond  to  the  Halphen  test,  and  the 
minority  that  did  respond  gave  so  faint  a  response  as  to  indicate  the  presence 
of  only  a  trace,  such  as  1  per  cent  or  less,  of  cotton  seed  oil. 

Richter  is  the  only  one  who  has  testified  on  this  point  for  defendant,  and  he 
does  not  undertake  to  say  the  presence  of  how  much  cotton  seed  oil  his  tests 
indicated,  sc  that  it  is  fair  to  assume  that  it  did  not  indicate  any  more  than  the 
trace  which  Morrison  testified  to.  It  is  admitted  and  asserted  by  defendant's 
circulars  that  Kream-Krisp  does  not  contain  any  unconverted  oil  at  all,  as  shown 
by  the  following  quotations: 

Kream-Krisp  although  made  exclusively  from  highly  refined  vegetable 
oil,  contains  no  oil  itself.  The  oil  is  completely  changed  by  hydrogenation 
under  the  influence  of  heat  to  a  butter-like  substance. 

Kream-Krisp  alt  nigh  made  from  highly  refined  vegetable  oil,  contains 
no  oil  itself.  The  oil  is  completely  changed  to  a  butter-like  substance. 

The  conclusion  is  that  even  if  Kream-Krisp  doe?  in  some  cases  respond  to  the 
Halphen  test  it  is  immaterial  both  from  the  standpoint  of  claims  1  and  2,  and 
from  the  practical  standpoint. 


In  almost  all  chemical  cases,  particularly  those  in  organic  chemistry,  one  side 
or  the  other  rambles  off  into  theoretical  and  impractical  considerations  which  are 
totally  unnecessary  for  the  decision,  and  which  the  experts  wrangle  about  until 
the  record  of  what  should  be  a  very  simple  matter  becomes  very  much  confused. 
We  are  sorry  to  say  that  this  case  is  no  exception  to  the  above. 


These  theories  in  this  case  are  embodied  in  the  triangular  charts  produced  by 
defendants'  expert,  upon  which  their  depositions  as  to  both  anticipation  and  non- 
infringement  are  based. 

Dr.  Baskerville  points  out  that  defendants'  triangular  charts  would  be  unobjec- 
tionable if  we  were  investigating  the  proportional  constituents  of  bodies  having 
only  three  components,  such  as,  linolin,  olein  and  stearin,  because  then  the 


EDIBLE  HYDROGENATED  FATS  641 

three  components  would  be  properly  represented  by  the  three  sides  of  the  tri- 
angle. But  where  the  proportions  of  components  are  under  consideration  in 
substances  having  more  than  three,  the  triangle  is  obviously  inappropriate,  and 
any  conclusions  based  upon  the  triangulation  must  be  misleading. 

The  proof  of  this  is  easy,  because  upon  a  moment's  consideration  it  will  be 
apparent  that  from  a  practical  standpoint,  defendants'  triangular  charts  resulted 
in  reductio  ad  absurdum. 

The  absurd  conclusion  is  reached  that  of  three  substances,  two  of  which 
(Crisco  and  Kream-Krisp)  are  semi-solid  and  one  of  which  (cotton  seed  oil)  is 
liquid,  the  two  semi-solid  substances  are  further  away  from  each  other  than  one 
of  them  is  from  the  liquid  substance. 


Dr.  Baskerville  summarizes  the  reason  why  he  chose  stearin  as  the  basis  of  his 
charts  as  follows,  Ans.,  309,  Rec.,  p.  775:  (1)  "  It  is  the  specific  substance  that 
is  mentioned  in  the  Burchenal  patent  to  bring  about  congealing  ..."  (2)  "  It 
is  known  to  be  the  factor  which  is  involved  in  making  lard  compounds  out  of 
these  hydrogenized  products."  (3)  "  It  is  quite  evident  that  what  we  obtained, 
the  results  have  shown,  is  in  accord  with  the  known  facts."  (4)  "  Olein  and 
linolin  are  liquids,  they  are  liquids  through  a  wide  range  of  temperatures,  and 
we  are  considering  here  substances  at  the  ordinary  temperatures." 

We  will  now  take  up  each  of  these  reasons  and  explain  it  more  in  detail. 

The  statements  of  the  patent  bearing  upon  Dr.  Baskerville's  first  reason  are 
as  follows: 

"  Saturated  fats,  however,  serve  the  purpose  of  congealing  the  shortening 
within  the  food,  and  thus  retain  it  equally  distributed  throughout  the  whole  " 
p.  1,  line  50. 

"  Sufficient  stearin  to  make  the  product  congeal  at  ordinary  temperatures " 
p.  1,  line  72. 

"  Enough  stearin  to  make  the  product  congeal  at  ordinary  temperatures " 
p.  2,  line  24. 

In  all  of  the  above  statements  the  congealing  or  semi-solidifying  which  is  the 
attribute  making  the  product  lard-like  is  associated  with  the  saturated  fats,  par- 
ticularly stearin,  which  represents  the  increase  of  saturated  fat  from  hydrogen- 
izing.  The  statement  first  above  quoted  that  the  saturated  fats  "  serve  the 
purpose  of  congealing  the  shortening  within  the  food,  and  thus  retain  it  equally 
distributed  throughout  the  whole  "  appears  from  the  testimony  to  be  the  very 
attribute  which,  from  a  practical  standpoint,  is  the  reason  why  the  semi-solid  or 
lard-like  shortening  is  preferred  by  cooks  to  the  liquid  shortening.  Every  wit- 
ness on  both  sides  who  has  mentioned  the  subject  has  said  that  the  liquid  is 
inferior  because  of  the  difficulty  in  getting  it  equally  distributed  throughout  the 
dough. 

Since,  therefore,  the  patent  specification  and  the  cook  agree  in  laying  so 
much  stress  upon  the  saturated  fats  and  their  congealing  or  semi-solidifying 
effect,  in  contradistinction  to  the  liquid,  there  is  certainly  every  reason  for 
dividing  the  product  into  the  solid  and  liquid  ingredients  in  making  a  chart. 

Dr.  Baskerville's  second  reason  is  that  the  saturated  fats  are  known  to  be 
the  factor  which  is  involved  in  making  lard  compounds  out  of  the  hydrogenized 
product.  What  he  means  here  is  that  in  the  mixtures  of  BurchenaFs  companion 


642  APPENDIX 

patent  No.  1,135,935  the  practical  value  of  the  mixture  over  and  above  liquid 
cotton  seed  oil  is  due  to  the  fact  that  the  liquid  ingredients  on  the  ore  hand  and 
the  solid  ingredients  on  the  other  hand  result  in  that  semi-solidity,  or  lard-like 
consistency,  or  congealed  condition  at  ordinary  temperatures,  which  proves  to 
be  so  desirable  in  mixing  the  dough. 

Dr.  Baskerville's  third  reason  is  that  the  result  he  has  shown  by  his  charts 
is  in  accord  with  the  known  facts.  He  means  here  that  we  know  that  Crisco 
and  Kream-Krisp  are  close  together  in  respect  to  their  semi-solid,  lard-like,  con- 
gealed at  ordinary  temperatures  condition,  and  that  a  chart,  as  his  does,  which 
brings  them  together  and  separates  them  on  the  one  hand  from  things  that  are 
liquid,  such  as  cotton  seed  oil,  and  things  that  are  solid,  on  the  other,  is  in 
accordance  with  the  known  facts.  Whereas  a  chart,  su^h  is  defendants',  which 
separates  the  semi-solid,  lard-like  bodies,  Crisco  and  Kream-Kriep,  and  brings 
either  of  them  together  with  a  liquid  body  like  the  oil,  is  in  opposition  to  known 
facts,  and  as  we  have  stated  above,  reduciio  ad  absurdum. 

Dr.  Baskerville's  fourth  reason  is  that  we  are  considering  here  substances  at 
the  ordinary  temperatures,  and  therefore  that  it  is  proper  to  divide  the  con- 
stituents between  those  that  solidify  below  ordinary  temperatures  and  those  that 
do  not. 

Our  adversary  will  refer  to  the  statement  of  the  patent  that  the  proportions 
are  high  in  olein  and  low  in  linolin. 

We  have  already  shown  by  the  file  contents  that  these  parts  of  the  specifica- 
tion were  inserted  with  claims  5,  6  and  7.  They  do  not  affect  claims  1  and  2. 

But  it  would  be  a  mistake  to  suppose  that  Kream-Krisp  is  not  in  the  direc- 
tion of  these  statements; — it  follows  them  to  a  degree. 

Comparing  Kream-Krisp,  Crisco  and  the  Burchenal  patent  product  with  the 
cottonseed  oil  from  which  they  are  obtained,  they  are  all  lower  in  linolin,  higher 
in  olein,  and  higher  in  stearin.  Defendant's  witness  Walker  admits  this  (Ans. 
46-51).  In  other  words,  relatively  to  the  cottonseed  oil  from  which  they  are 
obtained,  they  are  all  low  in  linolin,  high  in  olein,  and  with  enough  stearin  to  be 
congealed  or  semi-solid  at  ordinary  temperature. 

There  is  no  doubt  that  Kream-Krisp  would  be  better  if  it  more  nearly  com- 
plied with  the  proportions  of  the  patent.  If  it  were  higher  than  it  is  in  olein 
and  lower  in  linolin  it  would  be  less  liable  to  oxidation.  This  is  admitted  by  Dr. 
Walker,  Rec.,  p.  512,  Ans.  59,  and  is  testified  to  by  Morrison,  Rec.,  p.  782, 
Ans.  59.  But  the  fact  that  Kream-Krisp  is  an  inferior  following  of  the  patent 
does  not  relieve  it  from  infringement,  because  the  law  is  to  the  contrary. 


The  fundamental  error  of  the  attack  on  the  patent  from  the  chemical  side  is 
that  it  proposes  to  confine  the  invention  of  the  Burchenal  patent  to  his  preferred 
product  as  set  forth  in  claims  5  to  7,  and  entirely  fails  to  distinguish  between 
the  product  as  covered  in  claims  1  aid  2  and  the  preferred  form  of  the  claims 
not  in  issue. 

The  patent  has  to  do  with  chemically  changing  the  complex  glycerides  of  the 
vegetable  oil  so  as  to  vary  the  proportions  of  the  liquid  and  solid  components 
in  the  oil  itself,  and  thus  to  produce  a  food  product  semi-solid  and  lard-like.  It 
aims  to  produce  this  change  not  as  in  the  companion  Burchenal  patent  by  solidi- 
fying or  saturating  the  whole  body  of  oil  with  hydrogen  and  thus  obtaining  a 
semi-solid  by  dissolving  the  hard  material  in  additional  untreated  oil,  but  by 


EDIBLE  HYDROGENATED  FATS  643 

creating  the  necessary  solid  at  the  expense  of  the  liquids  in  the  oil  itself  until 
the  proper  consistency  of  lard  is  obtained.  This  conversion  and  chemical  change 
of  the  liquid  components  to  obtain  the  lard-like  product  is  the  essence  of  the 
patent  in  suit,  and  it  is  fully  and  properly  protected  by  the  first  two  claims. 
The  change  in  the  components  of  the  oil  could  not  be  protected  by  claims  more 
in  detail  which  specify  to  what  extent  the  components  should  be  changed,  or 
proper  protection  be  given  to  the  Burchenal  invention  in  issue  by  limiting  him 
to  specific  components,  as  is  abundantly  evidenced  in  this  very  case. 


The  point  was  to  raise  the  melting  point  of  the  original  oil  so  that  it  would  be 
semi-solid,  plastic  and  lard-like  at  normal  temperatures.  Burchenal  was  not 
concerned,  in  this  view  of  the  case,  with  whether  all,  or  a  large  part  of,  the  lin- 
olin  was  changed  to  olein  or  whether  the  linolin  was  less  reduced  and  the  olein 
less  increased  and  the  desired  consistency  was  obtained  by  increasing  the  stearin. 
The  new  product  must  have  those  proportions  of  liquid  and  solids  chemically 
created  by  the  treatment  to  give  the  desired  lard-like  quality.  The  change  in 
the  oil  itself  so  that  no  original  oil  remained  was  the  essential  thing.  To  what 
extent  the  components  were  changed  so  that  the  desired  product  was  obtained 
was  a  mere  matter  of  degree. 

There  were  a  number  of  old  methods  of  hydrogenating.  The  batch  methods 
of  Normann  &  Kayser,  the  continuous  methods  of  Bedford  &  Williams,  and 
Erdman.  In  Normann  &  Kayser,  the  hydrogen  bubbled  through  the  oil  and  the 
whole  mass  of  oil  and  catalyst  was  treated  continuously  with  the  hydrogen. 
In  the  Bedford  &  Williams  method  the  oil  was  run  through  or  over  the  catalyst 
supported  on  pumice  stone,  either  in  an  atmosphere  of  hydrogen  or  the  hydrogen 
was  sprayed  over  the  fixed  catalyst.  In  Erdman  the  oil  was  sprayed  by  the 
incoming  hydrogen  just  as  in  the  defendant's  apparatus  agairst  a  rotating  cylinder 
plated  with  the  catalyst,  and  the  treated  oil  was  then  run  through  a  body  of 
catalyst  in  the  bottom  of  the  vessel. 

All  of  the  old  methods  fully  saturated  the  materials  They  converted  all  of 
the  linolin  and  all  of  the  olein  into  stearin.  Burchenal,  through  Kayser,  was 
familiar  with  the  batch  method.  He  therefore  preferred  that  method  of  treat- 
ment. Burchenal,  however,  had  a  new  product  in  view.  He  did  not  change 
all  of  the  linolin  and  olein  to  stearin,  but  carried  on  the  conversion  until  he  had 
made  enough  solid  or  saturated  material  to  give  him  his  lard-like  hydrogenated 
food  product.  Because  the  hydrogenization  process  was  old  in  no  way  negatived 
the  novelty  of  his  new  product,  obtained  by  his  special  manipulation  of  that 
process. 

Burchenal  obtained  a  specific  product  high  in  olein,  low  in  linolin  and  with 
only  enough  added  stearin  to  give  the  proper  lard-like  material,  which  he  cov- 
ered in  claims  3-7.  If  Burchenal  had  preferred  the  Bedford  &  Williams  process, 
where  the  oil  is  passed  continuously  across  or  through  the  fixed  catalyst  sup- 
ported on  pieces  of  pumice,  he  would  have  obtained,  by  special  manipulation  of 
that  process,  a  product  which,  while  responding  fully  to  his  invention,  might 
probably  not  have  presented  the  specific  changes  called  for  in  the  specific  final 
claims  of  his  patent.  So,  if  he  had  preferred  the  Erdman  process  of  spraying 
the  oil  by  the  hydrogen  against  a  rotating  catalyzed  cylinder  and  he  had  spe- 
cially manipulated  that  process,  he  might  have  obtained  still  a  third  species  of 
his  invention. 


644  APPENDIX 

Then  Moore,  of  the  defendant  company,  in  order  to  make  the  Burchenal 
product  by  chemically  changing  the  component  glycerides  and  creating  sufficient 
stearin  to  obtain  the  desired  lard-like  consistency,  designs  a  modified  Erdman 
machine  of  the  continuous  Bedford  &  Williams  type.  In  this  machine  he  rotates 
a  spray  of  hydrogen  and  oil  over  a  fixed  diaphragm  of  catalyst,  and  in  this  way 
has  a  small  portion  of  the  oil  and  catalytic  nickel  in  contact  on  a  moving  pie- 
shaped  sector  portion  of  his  diaphragm,  say  about  ^  of  the  disk,  and  a  much 
greater  portion  of  his  oil,  catalyst  and  hydrogen  in  contact  through  the  remain- 
ing -£,  of  his  diaphragm. 

This  Moore  machine  was  designed  a  number  of  years  after  Burchenal  entered 
the  field,  and  for  the  very  purpose  of  producing  an  incompletely  hydrogenized, 
homogeneous,  lard-like  food  product.  Moore,  by  the  use  of  his  machine,  thus 
produces  exactly  the  product  of  the  patent,  but  he  obtains  a  different  specific 
change  in  the  components.  The  only  difference  between  the  product  produced 
in  the  Moore  machine  and  that  produced  by  Burchenal  is  the  degree  of  variation 
of  the  component  glycerides,  so  that  the  product  of  the  Berlin  Mills  Co.  is  not 
in  accordance  with  the  preference  of  Burchenal. 

THE  TRIANGULAR  CHARTS 

In  order  to  show  that  the  components  of  the  mixed  glycerides  in  defendant's 
product  are  different  from  the  specific  components  of  plaintiff's  patent,  a  fact 
which  we  do  not  and  never  have  denied,  the  defense  has  introduced  its  triangular 
charts  to  visualize  the  admitted  difference  between  the  species  of  product  of  the 
final  claims  of  the  patent  in  suit  and  the  species  of  defendant's  product,  both 
of  which  products,  however,  fall  directly  under  the  first  and  second  claims  of 
Barchenal,  which  claims  define  the  broad  and  fundamental  distinction  between 
the  patented  product  and  anything  which  preceded  it. 

The  triangular  chart  can  only  visualize  the  similarity  or  difference  between 
materials  having  three  components.  It  is  therefore  grievously  misleading  to 
attempt  to  compare  products  of  four  or  more  components  unless  we  can  group 
the  components  into  three  parts. 

The  essential  constituents  which  make  the  product  lard-like  as  distinguished 
from  a  liquid  are  the  added  hard  materials,  not  the  changed  proportions  of  the 
liquids.  The  defendant  has  used  its  charts  to  visualize  the  difference  in  the  pro- 
portions of  the  liquid  glycerides,  and  as  the  proportions  of  the  liquid  glycerides 
are  admittedly  different  the  defendant  is  able  to  place  plaintiff's  and  defendant's 
products  far  apart  on  its  charts,  but  at  the  same  time  it  has  been  forced  to 
demonstrate  how  untrustworthy  is  its  method,  because,  by  this  method  the  two 
semi-solids,  Crisco  and  Kream  Krisp,  are  located  very  much  further  apart  on 
their  charts  than  one  of  these  products  is  distant  from  the  liquid  cotton-seed  oil. 

If  the  triangular  chart  is  to  be  used  at  all  we  should  obviously  plot  the  three 
constituents  that  are  the  essentials  in  the  products  being  compared.  These  three 
essentials  are,  (a)  the  liquid  components,  (6)  the  original  hard  component  (not 
sufficient  to  alter  the  liquid  form),  and  (c)  the  added  hard  material  (which  is 
sufficient  to  convert  to  a  semi-solid  condition). 

In  order  to  compare  the  products  in  respect  to  these  essentials  the  plaintiff 
has  introduced  its  chart  IV,  which  is  identical  with  the  defendant's  charts  10 
and  14,  and  plaintiff  has  plotted  the  various  products  in  accordance  with  these 
essentials,  making  one  side  of  the  triangle  represent  the  ordinary  solid-fats, 


EDIBLE  HYDROGENATED   FATS  <  645 

another  side  the  added  solid  fats  and  the  third  side  the  liquid  fats  (as  the  plain- 
tiff did  not  have  the  enlarged  charts  of  defendants,  the  lines  which  divide  the 
defendant's  charts  10  and  14  are  not  all  placed  on  chart  IV.). 

As  indicated  on  chart  IV,  when  the  various  products  to  be  compared  are 
plotted,  the  cotton-seed  oil  (as  there  are  no  added  solid  fats)  appears  on  the  base 
line  and  the  Crisco  and  Kream  Krisp  products  measured  by  the  amount  of  added 
solids  are  brought  close  together  as  they  should  be,  while  Defendant's  Exhibit 
L  7,  which  is  not  any  recognized  or  intentional  product  of  the  prior  art,  appears 
some  distance  from  Kream  Krisp  and  Crisco,  and  with  the  Kayser  product, 
Exhibit  III,  near  the  top  of  the  chart. 

These  various  products  have  been  plotted  with  reference  to  an  average  cotton- 
seed oil  which  contains,  according  to  the  evidence,  about  21.5%  of  solid  fats. 

In  the  Burchenal  patent  a  cotton-seed  oil  of  only  17  per  cent  of  solid  fats  is 
mentioned  which,  from  the  Morrison  testimony,  would  appear  to  be  an  unusual 
oil,  as  produced  generally  in  this  country,  although  it  appears  that  the  pro- 
portion of  solid  fats  in  ordinary  cotton-seed  oil  of  commerce  ranges  from  18  per 
cent  to  25  per  cent. 

We  have  theretofore  indicated  on  chart  IV,  the  Burchenal  product  based  on 
this  rather  unusual  cotton-seed  oil  with  only  17  per  cent  of  solid  fat. 

It  seems  immaterial  to  discuss  whether  Burchenal  in  testing  the  cotton-seed 
oil  had  an  unusual  grade  or  not,  because  it  is  very  evident  from  the  specifica- 
tion that  what  he  proposed  was  a  product  in  which  from  3  per  cent,  of  solid 
fats  were  added  by  the  hydrogenization  in  order  to  give  the  desired  lard-like 
food  product.  The  patent  states: 

It  contains  from  20  per  cent,  to  25  per  cent,  of  fully  saturated  gly- 
cerids  .  .  .  while  the  cottonseed  oil  before  treatment  contained  17  per 
cent,  saturated  fats. 

It  therefore  seems  evident,  that  when  the  various  products  under  investigation 
are  plotted  with  reference  to  the  essential  components,  dividing  them  into  three 
parts,  that  is,  (a)  the  original  solid  fats,  (b)  the  added  solid  fats  and  (c)  the 
liquid  fats,  plaintiff's  product  Crisco  and  defendant's  product  Kream  Krisp  are 
brought  very  close  together  with  the  Kream  Krisp  actually  lying  between  the 
extremes  of  the  two  Crisco  products  in  evidence;  all  three  of  the  products  lying 
between  the  extremes  of  the  solid  fats  to  be  added  in  accordance  with  the  patent 
as  illustrated  in  Complainant's  Exhibit  Chart  IV. 

As  it  is  the  melting  point  taken  in  connection  with  the  added  solid  fats  that 
determines  the  semi-solid  character  of  the  patented  product  set  forth  in  claims 
1  and  2  and  determines  whether  the  product  of  the  defendant  comes  within  the 
limitations  of^the  terms  of  those  claims,  the  plaintiff  has  introduced  its  chart  V, 
in  which,  on  a  vertical  line,  it  has  indicated  the  percentages  of  added  solid  fats 
from  0  to  100,  and  on  a  horizontal  line  the  melting  points,  Centigrade  scale. 

In  chart  V  the  position  of  cotton-seed  oil  and  the  Crisco  products,  Kream 
Krisp,  the  Burchenal  product  based  on  a  cottonseed  oil  of  only  17  per  cent, 
original  solid  fats,  are  indicated  also  the  product  L  7  and  Kayser  Exhibit  3. 
By  running  a  line  through  the  proximate  positions  of  these  products  as  plotted 
on  chart  V,  we  obtain  a  curved  line  which  at  the  lower  end  approximates  to  the 
horizontal  and  at  the  upper  end  approximates  to  the  vertical,  giving  a  rather 
sharp  bend  between  a  range  of  melting  points  32  to  40  as  specified  by  Burchenal, 
and  showing  Kream  Krisp  and  Crisco  in  almost  the  same  location  at  the  most 


646  APPENDIX 

pronounced  portion  of  the  curve.  It  is  very  evident  from  an  examination  of 
this  chart  that  all  the  homogeneous,  lard-like,  semi-solid  products  will  fall  in  a 
little  group  at  the  bend  of  the  curve,  which  visually  indicates  the  transition 
point  from  liquid  to  semi-solid. 

There  is  still  another  method  of  comparing  the  patented  products  with  the 
product  of  defendant  (this  is  shown  in  Plaintiff's  chart  VI)  in  which  lines  are 
drawn  to  indicate  the  proportions  of  the  liquid  fats  and  the  solid  fats  in  the 
various  products,  all  that  portion  of  the  chart  lying  below  the  indicated  line  of 
any  particular  product  representing  the  solid  components,  and  that  portion  above 
the  line,  the  liquid  components.  Then,  by  taking  the  melting  points  of  the 
various  products  we  are  again  able  to  plot  these  products,  and  the  line  upon 
which  the  products  lie,  as  determined  by  the  melting  point,  is  the  same  as  the 
curved  line  illustrated  in  plaintiff's  chart  V. 

All  these  methods  lead  to  a  common  result,  that  is  to  say,  that  by  starting 
with  cotton-seed  oil  and  creating  in  the  oil  additional  solids,  by  partial  hydro- 
genation,  a  homogeneous  semi-solid  lard-like  product  is  produced. 


PRIOR  SHORTENING  MATERIALS 

The  defendant  has  taken  a  large  amount  of  testimony  to  prove  that  cotton- 
seed oil  itself  was  an  edible  product  and  had  been  used  extensively  for  cooking 
purposes,  and  also  that  compounds  of  cotton-seed  oil  with  beef  fats  (oleo-stearin) , 
had  been  very  largely  manufactured  and  sold  for  this  purpose.  The  object  of 
this  evidence  is  not  quite  clear,  but  we  assume  that  its  purpose  was  something 
derogatory  to  the  plaintiff's  case,  or  to  the  patentability  of  the  Burchenal  inven- 
tion. Neither  of  these  facts,  if  true  (and  we  have  no  reason  to  question  their 
truth),  is  material  to  the  present  case,  because  it  is  not  contended  that  either 
cotton-seed  oil  or  oleo-stearin  compounds  of  the  same,  anticipate  the  invention 
of  the  claims  in  suit.  It  has  never  been  contended  on  the  part  of  Burchenal 
that  he  first  suggested  the  use  of  cotton-seed  oil  either  as  an  edible  product  or 
as  a  cooking  material.  But  the  prior  knowledge  and  use  of  these  materials  do 
not  change  the  fact  that  Burchenal  produced  from  cotton-seed  oil  a  new  mate- 
rial which  has  enormously  extended  the  use  of  cotton-seed  oil  in  the  food  indus- 
try, and  which  has  large  advantages  over  its  use  either  alone  or  combined  with 
oleo-stearin.  Moreover,  the  partially  hydrogenated  product  of  the  patent  in 
suit  is  recognized  in  the  commercial  world  as  a  distinctly  different  product 
from  any  other .  cooking  material  on  the  market  (see  Richardson,  in  answer  to 
questions  by  the  Court). 

In  connection  with  this  evidence  of. the  prior  use  of  cottonseed  oil  and  oleo- 
stearin  compounds,  defendant  examined  Dr.  Bacon  as  to  the  subsequent  use  by 
the  Ward  Baking  Company  in  making  bread,  of  a  shortening  material  consisting 
of  hard  hydrogenized  cotton-seed  oil  like  plaintiff's  Exhibit  III.  finely  ground 
and  thoroughly  mixed  with  flour.  It  developed  in  the  course  of  the  cross-exam- 
ination of  Dr.  Bacon  that  this  material  was  patented  to  one  Esterbrook,  the 
patent  being  owned  by  the  Ward  Baking  Co.  From  the  claims  of  this  patent 
it  appears  that  the  invention  consisted  merely  of  comminuted  hardened  oil 
mixed  with  flour.  It  is  used  by  mixing  it  in  proper  proportions  with  the  flour 
of  which  the  bread  is  made.  The  evidence  with  regard  to  this  material  shows 


EDIBLE  HYDROGENATED  FATS  647 

that  it  was  not  equivalent  to  the  hydrogenated  product  of  the  patent  in  suit 
and  that  it  was  of  much  later  date,  Dr.  Bacon  testifying  that  the  Ward  Com- 
pany began  using  it  in  1914  or  1915. 

Both  the  cotton-seed  oil  and  the  Ward-Esterbrook  material,  one  a  liquid  and 
the  other  a  dry  powder,  require  to  be  mixed  very  thoroughly  with  the  flour 
with  which  it  is  combined  for  cooking,  and  the  merit  of  each  material  depends 
upon  the  thoroughness  of  this  mixing.  It  has  been  shown  by  the  testimony  of 
Miss  Hanko  on  the  part  of  plaintiff  in  rebuttal,  that  this  fact  constitutes  a  very 
great  objection  to  the  use  of  these  materials,  and,  while  it  is  possible  to  utilize 
them  for  shortening  material  in  place  of  lard  and  lard  compositions,  such  prac- 
tice is  not  within  the  range  of  the  patience  and  ability  of  the  ordinary  house- 
wife. 

The  most  serious  objection  to  the  use  of  the  liquid  cottonseed  oil  as  a  shorten- 
ing material  is  the  fact  that  it  affords  no  moisture  within  the  dough,  while  it 
decreases  by  50  per  cent,  the  amount  of  water  or  milk  required  to  make  the 
proper  consistency  of  the  batter,  and,  as  a  result,  the  steam  generated  in  cooking 
which  is  needed  for  raising  the  dough  to  give  it  its  light  and  flaky  character 
when  cooked,  is  absent.  The  consequence  is  that  it  is  necessary  to  use  expen- 
sive baking  powder  in  connection  with  the  oil  to  accomplish  this  result. 

As  to  the  hard  material,  it  cannot  be  used  in  frying  without  leaving  a  coating 
on  the  product,  and  the  hardened  material  is  indigestible  because  it  cannot  be 
acted  upon  in  the  digestive  processes  until  it  is  in  melted  condition.  If  it 
remains  unmelted  at  the  body  temperature,  all  the  authorities  hold  that  to  that 
extent  it  is  indigestible,  or  at  least  is  very  much  harder  to  digest  than  the  semi- 
solid  cooking  fats. 

It  plainly  appears  from  the  evidence  that  the  partially  hydrogenized  semi- 
solid  product  is  the  best  of  all  the  cooking  materials  discussed  in  the  case.  In 
Part  I.,  supra,  we  have  recited  from  the  patent  in  suit  various  advantages  it 
has  over  the  best  leaf  lard,  and  necessarily  therefore  over  compounds  of  cotton- 
seed oil  and  oleo-stearin.  Mr.  Morrison  was  examined  by  the  plaintiff  in  rebuttal 
on  these  points,  and  states  with  regard  to  such  advantages  that  in  his  opinion 
such  statements  of  the  patent  were  true  when  the  application  was  filed,  and 
that  they  are  also  true  to-day  (Morrison,  Rec.,  p.  782,  Qs.  61-70).  Thus,  he 
says  that  the  oil  does  not  make  the  best  shortening,  that  the  hard  fats  were 
not  as  digestible  as  liquid  fats,  that  the  semi-solid  of  the  patent  in  suit  ir.ore 
closely  resembles  lard  than  do  the  commercial  mixtures  of  cotton-seed  oil  and 
oleo-stearin,  that  in  many  respects  the  semi-solid  product  is  superior  to  leaf  lard 
as  a  shortening,  that  it  is  not  so  liable  to  become  rancid  and  that  the  product 
can  be  heated  to  a  considerably  higher  temperature  without  smoking  or  burning. 

The  testimony  of  Guy  B.  Taylor  as  to  the  commercial  introduction  and  gen- 
eral acceptance  of  plaintiff's  patented  product  shows  sales  rising  from  two  and 
half  million  pounds  during  the  latter  part  of  1911  progressively  from  year  to 
year  up  to  sixty  million  pounds  in  1916.  This  is  eloquent  testimony  to  the 
intrinsic  value  of  the  product  and  its  relative  merit  as  to  prior  and  competing 
materials. 

Defendant  is  not  in  a  position  to  assert  that  the  hydrogenized  semi-solid 
product  is  not  of  superior  merit  to  the  various  cooking  materials  to  which  the 
evidence  above  referred  to  relates,  for  in  its  pamphlets  in  evidence  it  takes  the 
ground  that  its  product  Kream  Krisp,  which  is  a  hydrogenized  semi-solid  made 
from  cotton-seed  oil,  is  superior  not  only  to  lard,  but  also  to  compounds  of 


648  APPENDIX 

cotton-seed  oil  and  oleo-stearin;  indeed,  to  all  other  shortening  materials  on  the 
market,  laying  particular  stress  upon  the  fact  that  it  will  not  turn  rancid,  does 
away  with  beef  stearin,  has  a  high  smoking  point,  is  free  from  adulteration  and 
contains  no  hard  fats  or  oil,  but  is  completely  changed  by  hydrogenization  to  a 
butter-like  consistency,  has  a  low  melting  point  and  is  easily  assimilated  by  the 
digestive  organs. 

No  evidence  has  been  offered  on  the  part  of  the  defendant  questioning  the 
merit  in  any  of  the  above  particulars  of  plaintiff's  patented  product  over  these 
prior  cooking  materials,  nor  has  it  been  claimed  that  defendant's  hydrogenized 
product  is  any  better  or  different  in  these  respects  from  that  of  the  plaintiff. 

We  think  it  is  quite  evident  that  not  only  is  this  testimony  offered  by  defend- 
ant in  regard  to  the  character  and  use  of  these  other  cooking  or  shortening 
materials,  wholly  immaterial  to  the  present  issue,  but  that  the  record  establishes 
the  superior  merit  of  the  plaintiff's  partially  hydrogenized  semi-solid  product, 
not  only  over  these  prior  materials,  but  also  over  the  best  leaf  lard  itself. 

CONCLUSION 

In  conclusion,  we  submit  that  Burchenal  was  the  first  to  conceive  and 
utilize  hydrogenated  cotton  seed  or  other  vegetable  oil  for  edible  purposes;  that 
he  was  the  original  and  first  inventor  of  an  homogeneous  lard  like  food  product, 
consisting  of  an  incompletely  hydrogenized  vegetable  oil,  as  set  forth  in  claims 

1  and  2  in  suit,  and  the  father  of  the  hydrogenized  oil  food  industry;    that  the 
plaintiff  was  the  first  to  introduce  the  said  food  product  into  public  use  and  has 
effected  a  very  wide  and  extensive  introduction  of  the  same  and  thereby  con- 
ferred a  great  benefit  on  the  public;    that  the  invention  set  forth  in  claims  1  and 

2  in  suit  is  new,  not  having  been  publicly  used,  or  patented,  or  described  in  any 
printed  publication,    prior  to   the    invention  or  discovery  there  by  Burchenal- 
that  the  claims  in  suit  are  not  limited,  either  by  their  own  terms,  or  by  the  prior 
art,  or  by  the  accepted  rules  of  construction,  to  the  specific  product  set  forth  in 
the  specification  and  claimed  in  the  other  claims  of  the  patent;    that  plaintiff 
by  reason  of  the  premises  is  entitled  to  a  broad  construction  of  said  claims  in 
suit;     that   defendant   by   the   manufacture   and   sale   of    "  Kream   Krisp "    has 
infringed  the  claims  in  suit;    and  that,  therefore,  the  plaintiff  is  entitled  to  a 
decree  as  prayed  in  the  bill. 

April  28,  1917. 

KERB,  PAGE,  COOPER  &  HAYWARD, 

Solicitors  for  Plaintiff. 
LIVINGSTON  GIFFORD, 
ALFRED  M.  ALLEN, 
THOMPSON  B.  KERR, 

Of  Counsel. 

(16261) 


EDIBLE  HYDROGENATED  FATS  649 


UNITED  STATES  DISTRICT  COURT. 
SOUTHERN  DISTRICT  OF  NEW  YORK. 


PROCTER  &  GAMBLE  COMPANY, 
Plaintiff. 

In  Equity,  No.  13-100. 
On  Burchenal  Patent  No.  1,135,351. 
BERLIN  MILLS  COMPANY, 

Defendant. 


BRIEF  FOR  DEFENDANT. 


JOHN  C.  PENNIE, 
Solicitor  for  Defendant. 

MARCUS  B.  MAY,  V 

JOHN  C.  PENNIE, 

Counsel  for  Defendant. 

.  ....  ;| 

FOREWORD 

This  case  involves  food  fats,  one  of  the  three  life  sustaining  elements,  which 
consist  of  proteins,  carbohydrates  and  fats. 

The  use  of  fats  and  oils  of  animal  and  vegetable  origin  is  primarily  that  of  a 
food,  although  to  a  more  limited  extent  such  fats  are  employed  for  the  manu- 
facture of  soap,  candles,  lubricants  and  illuminants.  Edible  fats  may  be  divided 
into  table  and  culinary  fats.  "Table  fats  are  those  like  butterc  and  table  oils, 
which  are  most  commonly  used  as  an  accompaniment  to  food  to  secure  a  desired 
flavor  or  texture,  and  culinary  or  cooking  fats  are  those  which  are  incorporated 
with  other  foods  (as  shortening)  or  used  as  a  medium  for  cooking  foods,  as  in 
frying." 

The  alleged  new  product  which  forms  the  subject  matter  of  the  patent  in  suit, 
belongs  to  the  second  class,  to  wit,  culinary  or  cooking  fats;  and 

it  is  at  last  an  article  which  pertains  to  the  cooking  art;  an  art,  if  it  may 
be  properly  called  an  art,  which  is  as  old  as  the  discovery  of  the  uses  of 
fire,  and  as  varied  in  its  exemplifications  as  the  sands  of  the  sea  .  .  . 

(Lurton,  C.  J.  in  Sanitas  Nut  Food  Co.  vs.  Voigt  139  Fed.,  551, 
553. 

It  is  said  to  be  a  "  food  product  consisting  of  a  vegetable  oil,  preferably  cot- 
tonseed oil,  partially  hydrogenized  and  hardened  to  a  homogeneous  white  or 
yellowish  semi-solid  closely  simulating  lard."  As  will  be  shown,  there  have  been 
on  the  market  for  many  years  as  staple  culinary  fats,  food  products  consisting 
of  cottonseed  oil  hardened  to  a  homogeneous  white  or  yellowish  semi-solid  closely 
simulating  lard  by  the  addition  of  stiffening  agents,  such  as  oleo-stearine  or  a 
hard  vegetable  fat.  As  illustrating  the  extent  to  which  such  "  lard  compounds  " 
or  "  lard  substitutes  "  as  they  are  called,  are  produced,  the  record  shows  that 


650  APPENDIX 

Swift -&  Company  alone  manufacture  and  sell  between  250,000,000  and  500,000- 
000  pounds  annually  of  such  food  products. 

The  stiffening  or  hardening  of  cottonseed  oil  by  hydrogenation  is  not  claimed 
as  new  in  the  patent  in  suit,  for  this  was  common  property,  and  semi-solid  fats 
produced  by  the  hydrogenation  of  cottonseed  and  other  vegetable  and  animal 
oils  were  also  common  property,  before  the  alleged  invention  of  the  patent  in 
suit,  as  the  patentee  concedes. 

In  the  very  nature  of  things  it  appears  at  the  outset  that  the  product  of  the 
patent  in  suit  involves  only  the  selection  of  a  known  fat  for  a  use  "  as  old  as  the 
discovery  of  the  uses  of  fire." 

PARTIES 

The  plaintiff,  Procter  &  Gamble  Company,  an  Ohio  corporation. 

*     *     * 

The  main  business  of  the  plaintiff  was  and  is  the  manufacture  of  soap,  and 
since  March,  1909,  it  has  been  also  engaged  in  the  manufacture  of  a  lard  sub- 
stitute (Flake  White)  which  however  is  not  the  alleged  new  product  of  the  patent 
in  suit,  and  since  May,  1911,  it  has  also  been  engaged  in  the  manufacture  of 
Crisco. 

The  defendant,  Berlin  Mills  Company,  is  a  Maine  corporation  having  mills 
at  Berlin,  New  Hampshire,  for  the  manufacture  of  paper  and  wood  pulp.  For 
the  purpose  of  utilizing  a  by-product — hydrogen — produced  in  the  manufacture  of 
bleach,  it  built  a  plant  for  the  hydrogenation  of  oils,  and  by  September,  1914, 
placed  upon  the  market  a  lard  substitute,  Kream  Krisp,  which  is  alleged  to 
infringe  the  patent  in  suit.  This  material  is  produced  by  a  novel  process  and 
apparatus  which  are  covered  by  defendant's  patents. 

DEFENSES 

In  this  case,  the  defendant  relies  upon  two  defenses,  to  wit: 

(1)  The  patent  in  suit  is  invalid  and  void;    and 

(2)  the  defendant's  product  does  not  infringe  the  claims  sued  on. 

Under  the  first  defense,  the  defendant  submits  that  the  patent  is  invalid  and 
void: 

(a)  because  the  patentee  failed  to  comply  with  the  provisions  of  Section  4888, 
U.  S.  Revised  Statutes,  which  require  such  a  written  description  of  the  product 
claimed  and  the  method  or  producing  it  as  will  enable  one  skilled  in  the  art 
without  experiment  ''to  make,  construct,  compound  and  use  the  same"; 

(b)  because  of  new  matter  inserted  in  the  specification  and  claims  during  the 
prosecution  of  the  application  which  resulted  in  the  issuance  of  the  patent  in  suit; 

(c)  because  if  there  be  any  modicum  of  invention  in  the  claims  of  the  patent 
in  suit — which  the  defendant  denies — it  is  not  the  invention  of  the  patentee, 
John  J.  Burchenal,  but  is  the  invention  of  Edwin  Cuno  Kayser,  who  disclosed 
it  to  said  Burchenal;    and 

(d)  for  want  of  patentable  subject-matter. 

Under  the  second  defense,  that  of  non-infringement,  the  defendant  urges: 
(a)  That  by  reason  of  restrictions  and  limitations  imposed  upon  the  specifica- 
tion and  claims  in  order  to  secure  their  allowance,  the  cluing  must  be  construed 


EDIBLE  HYDROGENATED  FATS  651 

narrowly  to  a  product  having  certain  definite  physical  and  chemical  constants 
different  from  those  of  defendant's  product — Krearn  Krisp; 

(b)  that  Kream  Krisp  is  not  a  homogeneous  lard-like  food  product  consisting 
of  incompletely  hydrogenized  vegetable   (cottonseed)   oil,  within  the  meaning  of 
the  claims; 

(c)  that  the  claims  must  be  limited  to  a  product  produced  by  the  process 
described  in  the  patent  specification,  and,  since  Kream  Krisp  is  produced  by  a 
different  process,  it  does  not  infringe;    particularly  as 

(1)  defendant's  process  cannot  produce  the  product  described  in  the  patent  in 
suit;    and 

(2)  the   process   described   in   the  patent   in   suit   cannot   produce   defendant's 
product. 

THE  PATENT  IN  SUIT 

The  patent  in  suit  to  John  J.  Burchenal,  No.  1,135,351,  was  applied  for  on 
November  10,  1910,  and  was  issued  April  13,  1915.  It  is  not  contended  that 
defendant  infringes  claims  3  to  7,  inclusive,  which  are  directed  to  the  product 
specifically  described  in  the  specification,  the  plaintiff  relying  only  on  claims  1 
and  2. 

The  specification  describes  a  process  of  hydrogenating  cottonseed  oil,  by  agi- 
tating a  mixture  of  oil  and  catalytic  nickel,  when  heated  to  a  temperature  of 
about  155°  C.  in  the  presence  of  an  atmosphere  of  hydrogen,  and  stopping  the 
reaction  when  the  product  on  cooling  is  a  white  or  yellowish  semi-solid. 

It  is  conceded  by  Burchenal  that  he  is  not  the  inventor  of  that  process  of 
hydrogenation  described  in  his  specification,  and  is  not  the  inventor  or  dis- 
coverer of  the  semi-solid  fatty  products  produced  by  such  process. 

The  Kayser  patents,  1,004,035  and  1,008,474,  which  are  conceded  to  be  prior 
art  by  Burchenal,  describe  in  detail  the  process  briefly  referred  to  in  the  Bur- 
chenal patent  specification  and  also  describe  the  production  of  both  solid  and 
semi-solid  products  of  any  desired  consistency  by  the  hydrogenation  of  cotton- 
seed oil.  Various  other  patents  and  publications  of  the  prior  art,  as  will  be 
shown,  describe  the  hydrogenation  of  cottonseed  and  other  oils  into  both  solid 
and  semi-solid  products  or  fats. 

The  Burchenal  patent  presents  no  claim  for  the  process  of  hydrogenation, 
and  no  claim  in  haec  verbis  for  "a  semi-solid  product  produced  by  the  hydro- 
genation of  cottonseed  or  other  vegetable  oil."  The  two  claims  in  suit,  however, 
specify 

A   homogeneous   lard-like   food   product    consisting   of   an   incompletely 
hydrogenized  vegetable  (cottonseed)  oil; 

and  by  referring  further  to  the  specification,  there  is  given  a  description  of  this 
specific  food  product,  to  wit:  one  "  which  is  high  in  olein,  low  in  linolin  and 
lesser  saturated  fats  and  with  only  enough  stearine  to  make  the  product  congeal 
at  ordinary  temperatures  "  page  2,  lines  22-27;  or,  more  especially,  one  con- 
taining "  twenty  to  twenty-five  per  cent,  of  fully  saturated  glycerids,  from  five 
to  ten  per  cent,  linolin  and  from  sixty-five  to  seventy-five  per  cent,  olein. 

The  specification,  however,  is  silent  as  to  any  method  for  producing  this 
particular  "  lard-like  "  food  product.  It  assumes  that  such  product  will  be  pro- 
duced by  the  particular  process  set  forth  in  lines  86-92,  page  1  of  the  specifica- 


652  APPENDIX 

tion.  It  assumes,  apparently,  that  the  semi-solid  product  produced  by  that 
process  will  be  subjected  to  the  same  treatment  that  fats  are  ordinarily  sub- 
jected in  making  lard  or  lard  compounds,  for  the  specification  describes  no  after- 
treatment  of  any  kind  to  give  to  the  product  the  salve-like  consistency  of  lard, 
or  the  appearance  of  Crisco,  so-called.  The  specification  does  not  suggest 
the  clarifying,  deodorizing,  refrigerating  and  aerating  processes  to  which  lard 
substitutes  are  subjected.  D.  R.,  70-71,  Qs488-495.  Nor  does  the  specifica- 
tion suggest  that  the  cottonseed  oil,  which  is  to  be  treated,  should  be  prelimi- 
narily refined.  The  percentage  of  catalyst  to  be  used,  and  the  extent  of  the 
pressure  of  hydrogen  in  the  hydrogenating  vessel  are  omitted.  All  these  matters 
are  treated  in  the  patent  as  immaterial,  the  only  directions  given  being  to  stop 
the  process  "  when  the  oil  has  been  converted  to  a  product  which  cools  to  a 
white  or  yellowish  semi-solid.  .  .  ."  A  dilemma  is  thus  presented.  Either  any 
white  or  yellowish  semi-solid  produced  by  the  hydrogenation  of  cottonseed  oil 
(for  example,  that  described  in  the  Kayser  patents  is  a  "  homogeneous  lard-like 
product,"  containing  20-25%  stearin,  65-75%  olein  and  5-10%  linolin;  or  else 
the  patent  fails  to  describe  how  the  product  is  to  be  produced,  in  accordance 
with  the  requirements  of  Section  4888,  U.  S.  Revised  Statutes,  as  will  be  here- 
inafter more  fully  elaborated. 

In  the  first  case  it  is  to  be  observed  that  the  patent  in  suit  while  referring  to 
"  a  vegetable  oil  "  or  to  "  other  vegetable  oil,"  actually  describes  the  treatment 
of  cottonseed  oil  only,  and  obviously  the  product  described  is  only  that  pro- 
duced by  hydrogenizing  cottonseed  oil,  or  else  the  semi-solid  products  pro- 
duced by  the  hydrogenation  of  all  vegetable  oils  must  have  the  proportions  of 
component  glycerides  recited  in  the  specification.  There  is  either,  therefore,  no 
difference  between  claims  1  and  2,  or  else  claim  1  is  for  an  abstraction — a  gen- 
eralization— and  as  such  is  void  or  invalid.  Claim  2  likewise  being  for  the  same 
product  which  is  defined  in  the  specification  as  having  the  certain  proportion  of 
component  glycerids  and  the  other  identifying  characteristics  noted  in  the  spe- 
cification, must  be  limited  thereto,  or  else  it,  too,  is  a  mere  abstraction  or  gen- 
eralization and  directed  to  what  is  manifestly  old  and  open  to  the  public  gen- 
erally. 


Where  the  patentee  fails  to  enlighten  those  skilled  in  the  art  how  to  practice 
the  invention  he  has  failed  to  promote  the  useful  arts,  because  when  his  patent 
expires  the  public  is  no  better  off  than  if  the  patent  had  never  been  granted. 

In  the  present  case,  as  we  shall  show,  the  patentee  not  only  seeks  to  exclude 
the  public  from  the  enjoyment  of  rights  which  the  public  had  acquired  from 
prior  inventors  and  discoverers,  but  seeks  to  do  this  on  a  patent  which  is  fatally 
defective, — first,  because  of  the  unlawful  inclusion  of  new  matter,  and,  second, 
because  the  patentee  has  failed  to  disclose  to  the  public  any  method  of  pro- 
ducing the  product  specifically  described  as  having  20-25%  stearin,  65-75% 
olein  and  5-10%  linolin  in  its  composition,  or  a  product  having  "  a  high  per- 
centage of  olein,  a  low  percentage  of  linolin  and  with  only  enough  stearin  to  cause 
the  product  to  congeal  at  ordinary  temperatures." 


The  record  fails  to  show  that  the  product  of  the  patent  in  suit  has  ever  been 
produced  commercially  even  by  the  plaintiff  itself. 


EDIBLE  HYDROGENATED  FATS  653 

Cmsco 

The  product  Crisco,  which  the  plaintiff  manufactures,  and  which  was  placed 
on  the  market  in  May,  1911,  admittedly  does  not  embody  or  contain  the  pro- 
portions or  percentages  of  compenent  glycerides  which  the  patentee  Burchenal 
specifies  in  his  patent.  The  affidavit  filed  by  Burchenal  on  March  5,  1917,  inti- 
mates that  the  product  as  originally  described  in  his  specification  as  filed,  "  would 
necessarily "  or  "  must  have "  (to  use  the  Examiner's  words)  the  composition 
20-25%  stearin,  65-75%  olein  and  5-10%  linolin;  and  Crisco,  therefore,  does 
not  contain  the  alleged  invention  of  the  patent  in  suit.  It  follows  that  the 
extent  to  which  Crisco  may  have  been  made  and  sold,  is  immaterial  to  the  pres- 
ent case. 

Furthermore,  Crisco  is  made  in  part  by  secret  processes — the  secrets  of  which 
are  "  jealously  guarded."  There  is  no  complete  statement  in  this  case  as  to  how 
"  Crisco  "  is  actually  manufactured.  Defendant's  counsel  were  denied  the  right 
to  see  it  made,  or  the  machinery  employed  in  its  production,  or  the  processes 
employed  in  its  manufacture;  and  no  one  but  the  plaintiff  knows  now  how  to  go 

about  it  to  produce  Crisco. 

*     *     * 

Morrison  conceded  that  Crisco  does  not  have  the  composition  recited  in  the 
patent  in  suit. 

Patent  in  Suit  Crisco 

range  range 

Stearin       20-25%  26  -27.3% 

Olein          65-75  57.8-52.9 

Linolin          5-10  16.2-19.8 

Crisco,  as  thus  conceded,  does  not  have  the  percentage  of  olein  (65-75%) 
and  the  percentage  of  linolin  (5-10%)  which  the  product  of  the  patent  in  suit 
"  must  necessarily  "  have,  and  is  not  the  alleged  new  product  of  the  patent  in 
suit. 

It  is  obvious,  therefore,  from  this  brief  survey  of  the  patent  in  suit,  which  will 
be  amplified  hereinafter  with  the  admissions  and  concessions  of  Burchenal  and 
other  officers  and  employees  of  the  plaintiff,  that  the  patent  is  a  menace  to  the 
public,  that  it  is  a  raid  on  the  public  rights,  and  that  the  Court  should  declare 
it  void. 

This  patent  in  suit  is  part  of  a  general  plan  to  deprive  the  public  of  any  right 
whatever  to  use  hydrogenized  fats  for  culinary  purposes.  The  plaintiff  has 
another  patent,  No.  1,135,935,  issued  to  Burchenal  on  April  13,  1915,  and  which 
was  filed  coincidently  with  the  patent  in  suit.  On  patent  No.  1,135,935,  a 
suit  has  been  brought  and  is  now  pending  against  Swift  &  Company  of  Chicago, 
Richardson,  XQ76,  T.  R.,  page  563.  That  patent  purports  to  cover  any  lard- 
like  edible  hydrogenized  oil  or  any  edible  product  comprising  a  mixture  of  any 
hydrogenized  oil  with  any  unhydrogenized  oil.  There  are  14  claims,  of  which  the 
first  four  read  as  follows: 

1.  A  lard-like  composition  comprising  edible  hydrogenized  fatty  oil. 

2.  A  lard-like  composition  comprising  edible  hydrogenized  vegetable  oil. 

3.  An  edible  oil  product,   comprising  hydrogenized  cottonseed  oil  and 
edible  oily  material  blending  therewith. 

4.  An   edible   oil   product   of   lard-like    consistency,    comprising   edible 
hydrqgenized  oil  and  edible  oily  material  blending  therewith. 


654  APPENDIX 

By  claiming  any  lard-like  "  edible  hydrogenized  fatty  oil "  and  any  oily  mix- 
ture containing  hydrogenized  oil  in  the  one  patent,  and  any  edible  lard-like 
"  partially  hydrogenized  vegetable  oil  "  in  the  patent  in  suit,  the  plaintiff  com- 
pany apparently  seeks  to  exclude  the  public  from  its  right  .to  use,  for  edible  or 
cooking  purposes,  any  hydrogenized  oil — and  yet  Burchenal  admittedly  did  not 
invent  any  process  of  hydrogenation  and  did  not  invent  or  discover  either  fully 
or  incompletely  hydrogenized  oil  products,  and  did  not  invent  anything  to  make 
such  products  available  for  edible  or  cooking  purposes. 

*  *     * 

One  of  the  chief  concerns  of  many  governments  to-day,  including  our  own,  is 
to  supply  their  people  with  food  fats  sufficient  to  sustain  life.  But  this  plaintiff 
is  seeking  to  make  private  gain  from  the  world  need.  It  asks  this  Court  to  aid 
it  in  excluding  from  the  use  of  the  public  as  food  products  those  fats  which  prior 
to  Burchenal's  appearance  had  already  been  dedicated  to  the  public  for  all  the 
purposes  to  which  they  might  be  put  by  those  men  to  whom  belongs  the  credit  of 
their  discovery  and  production. 

*  *     * 

In  reviewing  the  history  of  hydrogenation,  the  brief  states  olein  and  linolin 
are  both  liquids,  the  latter  having  a  solidification  point  much  lower  than  the 
former.  The  saturated  glycerides  are  solids,  and  are  soluble  in  the  unsaturated 
glycerides.  But  of  the  two  unsaturated  glycerides,  linolin  is  capable  of  dissolv- 
ing or  holding  in  suspension  a  greater  quantity  of  stearin  than  is  olein.  Hence, 
in  those  fatty  bodies  which  are  solid  or  semi-solid  at  ordinary  temperatures,  the 
stearin,  olein  and  linolin  are  in  such  proportion  that  the  stearin  is  not  in  sus- 
pension or  in  solution.  The  stearin  may  be  either  present  in  larger  proportion 
in  the  fat  than  in  the  oil;  or  the  linolin  may  be  so  decreased  and  consequently 
the  stearin  so  thrown  out  of  solution  as  to  solidify  the  mass. 

The  same  phenomenon  appears  when  cottonseed  oil,  which  consists  of  stearin, 
olein  and  linolin,  is  chilled.  As  the  solvent  power  of  the  olein  and  linolin 
decreases  with  the  lowering  of  the  temperature,  the  saturated  glycerides  appear 
visibly,  and  by  filtration  they  may  be  retained  in  the  filter  and  the  liquid  glycerides 
olein  and  linolin  separated  therefrom.  Now,  when  the  oil, — say,  for  example, 
cottonseed  oil,  which  consists  of  linolin,  olein  and  stearin  (stearin  and  palmitin 
grouped  together  as  "  stearin  "), — is  subjected  to  the  "  batch  method,"  or  Nor- 
mann  method,  of  hydrogenation,  the  linolin,  which  is  more  unstable  of  the  two 
unsaturated  glycerides,  because  it  has  two  double  bonds,  is  acted  on  first  and  is 
converted  to  olein.  If  the  hydrogenation  is  carried  on  long  enough,  however, 
the  olein  is  also  affected,  and  at  last  both  the  linolin  and  the  olein  are  converted 
into  stearin.  But  during  the  progress  of  the  reaction,  the  proportion  of  olein  is 
gradually  increased  with  the  corresponding  gradual  decrease  in  linolin,  and  the 
viscosity  of  the  oil  is  gradually  increased  until  it  assumes  a  semi-solid  condition. 
This  may  or  may  not  be  accompanied  by  an  increase  in  the  proportion  of 
stearin.  In  the  patent  in  suit,  for  instance,  the  preferred  semi-solid  product 
described  therein  is  said  to  consist  of  23%  stearin,  69.5%  olein  and  7.5%  lin- 
olin,— or  generally  20-25%  stearin,  65-75%  olein  and  5-10%  linolin.  It  is 
conceded  by  Dr.  Baskerville  that  cottonseed  oil,  according  to  an  analysis  given 
by  him,  may  consist  of  23.3%  stearin,  28.9%  olein  and  47.8%  linolin.  Hence, 
to  produce  the  preferred  product  of  the  patent  in  suit,  the  47.8%  of  linolin  in 
the  original  oil  must  be  reduced  to  7.5%,  and  the  28.9%  of  olein  in  the  original 


EDIBLE  HYDROGENATED  FATS  655 

oil  must  be  correspondingly  increased  by   (he  hydrogenation  to  69.5%,  and    this 
conversion  of  linolin  to  olein  should  produce  a  semi-solid  product. 


But  ordinarily  in  the  batch  process  of  hydrogenation,  while  the  proportion  of 
olein  is  being  rapidly  increased,  there  is  also  a  small  increase  in  the  proportion 
of  stearin.  This  is  shown  by  the  various  samples  produced  by  the  defendant — 
particularly  the  series  of  samples  L1,  et  seq.,  terminating  in  (Le)  and  (L7),  Ex- 
hibits A'B',  which  have  the  following  composition: 

L6  L7 

Per  cent  saturated  glycerides                         39.9  40.5 

Per  cent  olein                                                    56.2  55.6 

Per  cent  linolin                                                   3.9  3.9 

In  this  case,  starting  with  the  original  oil,  the  saturated  glycerides  have  been 
increased  from  23.3%  to  39.9%  in  one  case,  and  to  40.5%  in  the  other. 

The  extent  to  which  an  oil  or  fat  is  saturated  may  be  ascertained  by  finding 
how  much  iodine  will  be  taken  up  by  a  given  quantity  of  the  oil  or  fat,  for  the 
iodine  has  the  capacity  of  breaking  the  double  bonds  of  the  unsaturated  glycer- 
ides and  attaching  itself  thereto.  If  the  fatty  body  will  take  up  no  iodine,  it  is 
said  to  have  an  "  iodine  value  "  of  zero.  Oleic  acid  has  an  iodine  value  of  90. 
Linolic  acid  has  an  iodine  value  of  180;  i.e.,  by  reason  of  its  having  two  double 
bonds,  linolic  acid  can  take  up  twice  as  much  iodine  as  oleic  acid  which  has  but 
one  double  bond.  Cottonseed  oil  has  an  iodine  value  of  108  to  110,  and  the  liquid 
fatty  acids  of  cottonseed  oil  (i.e.,  the  mixture  of  oleic  acid  and  linolic  acid  after 
they  have  been  separated  from  their  glycerine  molecules)  have  an  iodine  value 
of  147  or  148.  Incidentally,  one  knowing  the  iodine  value  of  the  original  oil 
or  fat,  and  the  iodine  value  of  its  liquid  fatty  acids,  is  able,  by  a  simple  mathe- 
matical formula,  to  ascertain  the  proportions  of  linolin,  olein  and  saturated  gly- 
cerides of  such  original  oil  or  fat.  One  of  the  ways,  therefore,  in  which  an  oil 
or  fat  is  recognized,  is  by  ascertaining  its  iodine  value,  as  oils  and  fats  have 
certain  characteristic  or  identifying  values. 


The  various  common  oils  and  fats  used  for  food  or  culinary  purposes  consist 
mainly,  as  already  stated,  of  the  glycerides  of  linolic  and  oleic  acids  and  the 
glycerides  of  the  saturated  acids,  palmitic  and  stearic,  which  are  commonly 
grouped  together  and  termed  stearin. 

There  are  traces  of  the  glyceride  of  arachidic  acid  in  cottonseed  oil,  but  ara- 
chidic  acid  is  a  saturated  acid  and  its  glyceride  is  grouped  with  those  of  the  other 
saturated  acids  under  the  term  "  stearin  "  or  saturated  fats. 

The  proportions  in  which  these  component  glycerides  are  found  in  the  various 
oils  and  fats  differ.  In  lard,  for  example,  we  find  43%  saturated  glycerides, 
8  to  10%  linolin,  and  48  to  50%  olein,  in  olive  oil,  about  11%  stearin,  8% 
linolin,  and  81%  olein. 

*     *     * 
THE  PRIOR  ART 

The  catalytic  hydrogenation  of  oils  was  first  described  by  Dr.  Wilhelm  Nor- 
mann  in  British  patent  No.  1515  of  the  year  1903  (Defendant's  Ex.  Book  page 


656  APPENDIX 

94)  and  in  the  corresponding  German  patent  to  LePrince  &  Siveke  No.  141,029, 
Published  May  4,  1903  (Ex.  Book  page  102).  There  is  no  corresponding  United 
States  patent,  and  the  hydrogenation  of  oils  in  accordance  with  the  Normann 
process  and  the  products  produced  thereby  are  accordingly  public  property  in 
this  country. 

Dr.  Normann,  in  his  patents,  refers  to  the  prior  work  of  Sabatier  and  Sen- 
derens  in  hydrogenating  various  unsaturated  hydro-carbons,  and  then  states, 
beginning  at  line  27  of  page  2. 

I  have  found,  that  it  is  easy  to  convert  by  this  catalytic  method 
unsaturated  fatty  acids  into  saturated  acids.  ...  It  is  sufficient,  how- 
ever, to  expose  the  fat  or  the  fatty  acid  in  a  liquid  condition  to  the  action 
of  hydrogen  and  the  catalytic  substance. 

For  instance,  if  fine  nickel  powder  obtained  by  reduction  in  a  current 
of  hydrogen,  is  added  to  chemically  pure  oleic  acid,  then  the  latter  heated 
over  an  oil  bath,  and  a  strong  current  of  hydrogen  is  caused  to  pass 
through  it  for  a  sufficient  length  of  time,  the  oleic  acid  may  be  com- 
pletely converted  into  stearic  acid. 

The  quantity  of  the  nickel  thus  added  and  the  temperature  are  imma- 
terial and  will  only  affect  the  duration  of  the  process.  Apart  from  the 
formation  of  small  quantities  of  nickel  soap,  which  may  be  easily  decom- 
posed by  dilute  mineral  acids,  the  reaction  passes  off  without  any  secon- 
dary reaction  taking  place.  The  same  nickel  may  be  used  repeatedly. 
Instead  of  pure  oleic  acid,  commercial  fatty  acids  may  be  treated  in  the 
same  manner.  The  yellowish  fatty  acids  of  tallow,  which  melt  between 
44  and  48°  C.  and  whose  iodine  number  is  35.1,  will,  after  hydrogenation, 
melt  between  56.5  and  59°  C.  while  their  iodine  number  will  be  9.8  and 
their  colour  slightly  lighter  than  before,  and  they  will  be  very  hard. 

The  same  method  is  applicable  not  only  to  free  fatty  acids,  but  also 
to  their  glycerides  occurring  in  nature,  that  is  to  say,  to  fats  and  oils. 
Olive  oils  will  yield  a  hard  tallow-like  mass;  Unseed  oil  and  fish  oil  will 
give  similar  results  "  (Italics  ours). 

*  *     * 

Normann  describes  his  final  product,  produced  by  this  progressive  reaction 
from  olive  oil,  as  a  hard  "  tallow-like  "  mass.  Ordinary  tallow,  as  Dr.  Bacon 
points  out,  is  of  a  somewhat  semi-solid  character,  comparable  with  lard, 
and  is  one  of  the  common  evoking  fats.  Hence,  Normann  describes  his  final 
products  by  comparison  with  a  common  food  fat,  and  Dr.  Bacon  has  testified  to 
the  fact  that, — 

If  an  edible  olive  oil  was  started  with,  one  would  certainly  obtain  an 
edible  hydrogenated  product. 

*  *    * 

Dr.  Bacon  has  also  testified  that  the  Normann  process  is  a  commercial  process 
which  he  has  seen  in  use  in  this  country  on  a  commercial  scale,  and  he  is  cor- 
roborated in  this  by  Dr.  Richardson.  The  underlying  and  pioneer  nature  of  the 
Normann  patent  and  process,  upon  which  the  world-wide  industry  of  hydrogenized 
oils  is  based  (whether  these  hydrogenized  products  be  used  for  food,  soap,  candles, 
lubricants,  or  other  purposes)  has  been  emphasized  by  counsel  for  the  plain- 
tiff in  his  cross-examination  of  defendant's  expert,  Dr.  Bacon. 


EDIBLE  HYDROGENATED  FATS  657 

Normann,  in  his  patent,  does  not  describe  the  purposes  for  which  his  hydro- 
genated  fats  are  intended  but  leaves  them  to  be  inferred  by  those  skilled  in  the 
oil  and  fat  industry. 

*  *     * 

Dr.  Bacon  has  testified  also  that  at  the  Larkin  plant  various  degrees  of  hard- 
ness and  of  saturation  are  obtained  in  the  commercial  practice  of  the  Normann 
process,  and  that  these  products,  although  edible,  are  nevertheless  used  for  soap 
purposes. 

*  *     * 

The  brief  then  refers  to  Sabatier  and  Senderens  work  and  to  the  Bedford 
thesis. 


Fokin,  in  his  first  publication  of  1906  (J.  Russ.  Phys.-Chem.  Soc.  Vol.,  38, 
pages  419-446),  describes  first,  the  hydrogenation  of  oleic  acid  and  other  fatty 
acids  to  various  consistencies  and  degrees  of  incomplete  hydrogenation.  In 
experiment  28,  he  also  describes  the  hydrogenation  of  almond  oil  and  he  states 
that  after  one  hour  be  obtained  a  product  of  30°  titer  (page  26  of  translation, 
Ex.  F).  As  the  result  of  this  experiment,  with  almond  oil  Fokin  concludes: 

Thus,  the  reaction  proceeds  with  glycerides  also. 

In  his  second  article  of  1906  (ibid,  Vol.,  38,  pages  755-758),  Fokin  further 
describes  the  hydrogenation  of  unsaturated  fatty  acids  and  glycerides,  by  carry- 
ing out  the  hydrogenation  under  pressure.  With  respect  to  the  glycerides,  he 

states: 

The  reduction  of  glycerides  proceeds  worse  than  that  of  free  acids 
but  nevertheless  it  is  not  difficult  to  convert  linseed  oil  or  any  other  drying 
oil  whatever  into  substances  with  small  iodine  numbers,  at  first  into 
products  of  the  type  of  sunflower  oil  or  poppy  oil,  and  then  into  products 
analogous  to  sesame  oil  or  cottonseed  oil. 

Almond  and  olive  oil  undergo  a  metamorphosis  into  fats  corresponding 
to  beef  or  mutton  drippings. 

Oils  with  large  iodine  numbers  require  a  longer  time,  but  at  the  final 
end  they  also  give  solid  fats.  (Italics  ours). 

Dr.  Bacon  points  out  that  "  beef  and  mutton  drippings  is  what  is  known  as 
beef  tallow  and  mutton  tallow;  that  is,  the  rendered  fat  of  beef  or  mutton," 
and  that  such  products  are  "  very  close  to  the  lard  range  in  melting  point  and 
actually  used  by  many  people  for  cooking  and  shortening  purposes." 

Dr.  Bacon  also  points  out  that  the  iodine  values  of  linseed  oil,  sunflower  oil, 
and  cottonseed  oil,  are  respectively  about  185,  120  and  110,  so  that  when  Fokin 
describes  the  conversion  of  linseed  oil  into  products  of  the  type  of  sunflower 
oil  and  then  into  products  analogous  to  cottonseed  oil,  and  finally  into  sub- 
stances with  small  iodine  values,  he  is  describing  a  progressive  reaction  and 
degrees  of  hydrogenation  far  short  of  completion.  T.  R.  673.  The  above  quo- 
tation from  Fokin  thus  shows  a  clear  appreciation  by  him  of  the  gradual  and 
progressive  nature  of  the  reaction,  resulting  in  the  gradual  and  progressive  low- 
ering of  the  iodine  value,  with  the  formation  of  various  intermediate  products 
which  were  comparable  with  natural  products  of  like  iodine  values;  and  Fokin 


658  APPENDIX 

clearly  indicates  that  the  various  vegetable  oils  (including  linseed,  olive  and 
almond)  will  give  upon  hydrogenation  not  only  oils  of  lower  iodine  values  but 
also  solid  and  semisolid  fats  and  products  with  small  iodine  values.  Fokin  thus 
describes  clearly  the  production  of  intermediate  products  of  all  degrees  of  hydro- 
genation, from  the  original  oil  to  the  final  hard  fat,  as  a  necessary  and  inevitable 
consequence  of  his  process  of  hydrogenation. 

In  this  second  Fokin  publication,  Fokin  also  describes  the  hydrogenation  of 
oleic  acid  to  various  degrees  of  saturation,  and  to  products  of  various  solidifying 
points,  e.g.,  54.5°,  46.5°,  32-24°,  61°,  45-44°,  64-62°. 

In  his  third  article,  published  in  1907,  Defendant's  Ex.  Book,  page  114  Fokin 
further  describes  the  hydrogenation  of  oleic  acid,  croton  oil  and  almond  oil.  In 
the  case  of  oleic  acid  he  describes  several  experiments  which  show  the  gradual 
and  progressive  nature  of  the  reaction  and  the  gradual  and  progressive  conversion 
of  oleic  acid  into  a  product  of  progressively  increasing  content  of  stearic  acid, 
the  actual  percentage  of  stearic  acid  produced  being  stated  after  various  time 
intervals. 

In  his  fourth  article,  published  in  1908  Ex.  F,  Fokin  further  describes  the 
gradual  and  progressive  nature  of  the  hydrogenation  of  fatty  acids  and  glycerides, 
giving  many  examples,  and  showing  that  the  absorption  of  hydrogen  is  gradual 
and  progressive.  In  fact,  Fokin  measured  the  progress  of  the  reaction  and  found 
it  to  be  of  such  a  progressive  nature  that  it  is  capable  of  representation  graph- 
ically by  plotting  curves.  These  curves  are  found  on  pages  307  and  313  of 
the  original  Russian  article  (J.  Russ.  Phys-Chem.  Soc.  Vol.,  40)  and  on  page 
1497  of  the  German  article  (Zeit.  Angew.  Chem.  Vol.,  22).  In  experiments,  16 
and  17,  of  this  fourth  article,  Fokin  describes  the  hydrogenation  of  sunflower 
oil,  also  an  edible  oil  and  shows  that  it  also  undergoes  a  gradual  and  progressive 
hydrogenation,  as  indicated  by  the  hydrogen  absorption. 

In  their  British  patent  No.  2520  of  1907,  Bedford  and  Williams  describe  the 
catalytic  hydrogenation  of  various  organic  substances,  including  fatty  acids  and 
their  esters.  They  note  that  the  hydrogenation  of  oleic  acid  results  in  the 
bleaching  of  the  product,  as  well  as  its  hydrogenation;  and  they  point  out  that 
the  product  of  their  process  is  white  and  requires  no  further  treatment  (page  4, 
lines  13-16).  With  respect  to  linseed  oil  (a  vegetable  oil),  they  state — 

Linseed  oil  is  converted  in  a  solid  with  solidifiying  point  53°  C. 


On  July  11,  1908,  Paal  &  Roth  published  an  article  in  the  Berichte  der 
Deutschen  Chemischen  Gesellschaft  (Vol.  41,  pages  2283-2291)  in  which  they 
describe  the  hydrogenation  of  fatty  acids  and  glycerides  with  the  aid  of  col- 
loidal palladium  as  a  catalyst.  Touching  the  reduction  or  hydrogenation  of 
glycerides,  they  state  Defendant's  Ex.  Book,  pages  122,  123): 

The  Reduction  of  the  Fats. 

The  animal  and  vegetable  fats  and  oils  are,  as  is  well  known,  mixtures 
of  the  glycerine  esters  of  saturated  and  unsaturated  fatty  acids;  some  of 
them  contain  in  addition  the  glycerine  esters  unsaturated  oxy-fatty  acids. 
The  ratio  in  which  the  glycerine  esters  are  present  in  the  separate  fats 
is  only  relatively  constant,  it  varies  within  certain  limits.  All  fats  with- 
out exception  contain  glycerides  of  unsaturated  acids  in  the  presence  of 
glycerides  of  the  saturated  acids.  The  amount  of  glycerides  of  unsat- 


EDIBLE  HYDROGENATED  FATS  659 

urated  acids  is  determined  on  the  basis  of  the  quantity  of  iodine  or  chlor- 
ine which  they  will  take  up. 

The  Hubl  Iodine  Number,  which  gives  the  quantity  of  iodine  in  per 
cent  of  the  amount  of  fat  under  certain  definite  conditions  and  which 
in  food  chemistry  plays  an  important  part  in  detecting  adulteration  and 
in  the  identification  of  the  fats,  is  within  certain  limits,  constant  for  each 
individual  fat.  According  to  the  amount  of  glycerides  of  unsaturated 
acids  contained  in  a  fat  the  iodine  numbers  of  different  fat  varies  between 

8  and  180%. 

*     *     * 

The  above-described  transformation  of  oleic  acid  into  stearic  acid  led 
us  to  expand  our  experiments  to  include  the  fats  also.  We  chose  as  our 
starting  material  at  first  two  vegetable  fats,  castor  oil  and  olive  oil,  and 
an  animal  fat,  cod  liver  oil,  which  have  high  iodine  numbers  and  are 
therefore  rich  in  unsaturated  fatty  acids.  .  .  .  By  measuring  the  quan- 
tity of  hydrogen  absorbed  and  by  determining  the  iodine  number  of  the 
reduced  fats,  by  the  process  usually  employed  in  food  chemistry,  we  could 
follow  the  progress  of  the  hydrogenation  and  determine  the  end  of  the  pro- 
cess. (Italics  ours.) 

Paal  &  Roth  describe  several  experiments  where  they  did  in  fact  follow  the 
progress  of  the  reaction  and  noted  the  amounts  of  hydrogen  absorbed  at  periodic 
intervals,  the  same  as  did  Fokin  in  his  1908  publication.  Paal  &  Roth  started 
their  hydrogenation  at  ordinary  temperature,  and  followed  it  until  the  hydro- 
genation stopped,  and  they  found  it  was  necessary  then  to  heat  the  reaction 
vessel  to  make  the  reaction  continue.  They  explain  this  as  follows: 

An  explanation  of  the  effect  of  heating  can  be  found  in  the  fact  that  as 
the  hydrogenation  takes  place,  the  product  formed  is  solid  at  the  ordinary 
temperature  and  separates  out  in  the  form  of  crystals  which  hinder  the 
action  of  the  colloidal  palladium  upon  the  oil.  By  heating,  the  crystals 
are  liquefied  and  the  hydrogenation  again  starts. 

This  explanation  is  in  connection  with  the  hydrogenation  of  olive  oil,  and  not 
only  does  it  show  an  appreciation  of  the  gradual  and  progressive  nature  of  the 
process,  but  it  also  shows  that  of  necessity  there  was  obtained  by  this  reaction 
a  semi-solid  and  incompletely  hydrogenated  product,  solidifying  at  ordinary 
temperatures,  but  far  from  being  completely  hydrogenated;  for  even  after  heat- 
ing and  further  hydrogenation  they  obtained  from  the  olive  oil  a  product  still 
incompletely  hydrogenated  which  softened  at  43  and  melted  at  47.  They  state — 

The  iodine  number  of  the  hydrogenated  fat  was  9;  this  shows  that 
the  original  oil  had  been  hydrogenated  to  a  considerable  degree  but  that 
complete  hydrogenation  had  not  taken  place  by  any  means. 

In  their  second  article  of  May  8,  1909,  in  the  same  publication  (Vol.  42,  1541 
to  1553),  Paal  &  Roth  further  describe  their  work,  and  state, — 

Besides  castor  oil,  and  olive  oil,  which  were  studied  in  our  first  com- 
munication, we  have  experimented  with  the  vegetable  fats,  croton  oil, 
sesame  oil,  cottonseed  oil,  linseed  oil,  as  well  as  animal  fats  as  represented 
by  butter,  lard  and  oleomargarine.  With  these  fats  also  it  was  rare  that 


660  APPENDIX 

we  could  at  once  accomplish  a  complete  hydrogenation  down  to  an  iodine 
number  of  0.  But  when  the  partially  hydrogenated  fats  were  subjected 
to  another  reduction,  it  was  possible,  in  most  cases,  to  accomplish  com- 
plete hydrogenation. 

In  addition  to  thus  emphasizing  the  progressive  nature  of  the  hydrogenation, 
and  pointing  out  that  products  of  greater,  as  well  as  of  lesser,  degrees  of  incom- 
plete hydrogenation  are  possible,  they  note  the  improved  properties  of  the 
hydrogenated  fats,  as  to  their  rancidity, — 

In  contrast  to  the  natural  fats,  which  on  standing  naturally  become 
rancid  more  or  less  rapidly,  the  hydrogenated  fats  show  an  extraordinary 
stability.  After  being  kept  for  six  months  or  a  year  in  loosely  stoppered 
bottles  they  remained  entirely  unchanged  and  had  no  rancid  odor  or  taste. 

With  respect  to  croton  oil,  these  authors  note, — 

The  reduced  fat  had  entirely  lost  the  terrible  burning  taste  of  croton  oil. 

Not  only  did  they  thus  taste  the  product,  but  they  studied  the  physiological 
action  of  the  partially  and  completely  hydrogenated  croton  oil  and  found  that 
the  hydrogenation  had  converted  the  poisonous  croton  oil  into  a  hydrogenated 
product  which 

when  administered  internally  in  a  very  large  dose  caused  no  diarrhoea  or 
inflammation  with  a  rabbit  or  with  a  dog, 

and  hence  was  non  poisonous. 

With  olive  oil,  Paal  &  Roth  repeated  the  hydrogenation,  in  the  same  pro- 
gressive manner  described  in  their  1908  article,  carrying  out  the  reaction  in  two 
stages.  During  the  first  stage  the  iodine  value  was  reduced  from  81  to  39.7 
(about  half  way)  and  during  the  second  stage  from  39.7  to  zero.  The  gradual 
and  progressive  nature  of  the  process  is  emphasized  by  the  fact  that  the  complete 
hydrogenation  required  29  hours  time. 

With  sesame  oil,  Paal  &  Roth  followed  the  progress  of  the  hydrogenation  by 
noting  the  hydrogen  absorption  at  various  time  intervals. 

Cottonseed  oil  was  similarly  hydrogenated,  and  with  it,  as  with  the  other  oils, 
the  reaction  progressed  at  ordinary  temperatures  until  "  the  fat  globules  began  to 
solidify  out,"  whereupon  the  reaction  vessel  was  warmed  and  the  progress  of  the 
reaction  continued.  Thus  with  cottonseed  oil,  as  with  olive  oil,  Paal  &  Roth 
describe  the  production  of  incompletely  hydrogenated  products  solidifying  at 
ordinary  temperatures. 

Paal  &  Roth  note  also  that  the  hydrogenated  cottonseed  oil  fails  to  respond 
to  the  Halphen  test. 

They  also  hydrogenated  butter,  lard  and  oleomargarine,  three  of  the  best 
known  food  fats.  The  hydrogenized  butter  had  "  a  slight  pleasant  nut-like 
taste  "  and  "  after  standing  nine  months  there  was  no  sign  of  any  change  in  the 
product."  Another  hydrogenated  butter  had  a  melting  point  of  39.5-41  and 
an  iodine  value  of  13.6,  and  it  was  therefore  a  semi-solid  and  incompletely 
hydrogenated. 

Paal  &  Roth  thus  hydrogenated  most  of  the  common  oils  and  fats  used  for 
food  purposes.  They  noted  the  freedom  from  rancid  taste  and  odor  of  the 
hydrogenated  fats  even  after  long  standing.  Only  in  the  case  of  the  poisonous 


EDIBLE  HYDROGENATED  FATS  661 

croton  oil  did  they  consider  it  necessary  to  make  a  direct  statement  of  their 
physiological  tests  (made  in  the  usual  manner  in  which  such  tests  are  com- 
monly made  to  ascertain  whether  a  product  is  poisonous  or  edible)  and  in  this 
•asc  they  observed  that  the  hydrogenated  product  was  no  longer  poisonous  but 
was  rendered  innocuous  by  the  hydrogenation.  They  also  called  attention  to 
the  absence  of  "  the  terrible  burning  taste  of  croton  oil "  in  the  hydrogenated 
product. 

*  *     * 

Erdmann,  in  his  German  patent  No.  211,669  of  1907  (published  July  13,  1909). 
Defendant's  Ex.  Book,  page  105,  describes,  in  Example  3,  the  hydrogenation  of 
a  low  melting  tallow  of  solidification  point  31°  into  a  harder  tallow  of  solidifi- 
cation point  38°,  which,  as  Dr.  Bacon  points  out,  is  a  product  "  still  very  far 
short  of  complete  hydrogenation."  Completely  hydrogenated  tallow  would  have 
a  solidification  point  of  about  55  or  60°.  Tallow,  as  pointed  out  by  Dr.  Bacon, 
is  one  of  the  common  food  fats. 

KAYSER 

Edwin  Cuno  Kayser  is  the  patentee  of  U.  S.  patents  No.  1,004,035,  granted 
September  26,  1911,  on  an  application  filed  March  20,  1908,  and  No.  1,008,474, 
granted  November  14,  1911,  on  an  application  filed  Feb.  18,  1910.  Both  patents 
were  granted  to  The  Procter  and  Gamble  Company  (the  present  plaintiff)  as 
assignee  and  have  since  been  transferred  to  the  Hydrogenation  Company.  Q258- 
262,  D.  R.,  page  35.  The  applications  for  these  patents  were  prosecuted  before 
the  Patent  Office  by  the  same  attorneys  who  prosecuted  the  application  of  the 
Burchenal  patent  in  suit,  as  appears  from  the  file  wrappers  in  evidence,  Ex.  G 
and  H,  and  both  applications  were  filed  long  before  the  filing  of  the  application 
for  the  Burchenal  patent  in  suit.  These  Kayser  patents  will  expire  some  four 
years  prior  to  the  expiration  of  the  Burchenal  patent  in  suit,  and  the  right  to 
practice  the  processes  of  these  patents  and  to  produce  the  products  of  such 
processes  will  then  become  public  property. 

Burchenal  has  testified  that  the  Kayser  applications  were  filed  with  his  knowl- 
edge and  approval,  and  he  has  expressly  disclaimed  inventorship  of  any  of  the 
processes  or  parts  thereof  described  in  the  specifications  of  these  two  Kayser 
patents. 

*  *     * 

Kayser  came  to  this  country  in  November  of  1907,  and  went  immediately  to 
Cincinnati,  where  he  began  negotiations  with  the  Procter  &  Gamble  Company, 
through  their  General  Manager  Burchenal,  to  interest  the  Procter  &  Gamble 
Company  in  a  process  which  he  had  manipulated  for  some  three  years;  a  process 
which  he  said  he  alone  was  thoroughly  familiar  with,  and  which  was  "  of  the 
greatest  possible  importance  to  soap  manufacturers,"  the  Procter  &  Gamble  Co. 
being  then  soap  manufacturers.  It  appears  that  Kayser  began  his  work  on  the 
catalytic  hydrogenation  of  oils  in  1904,  a  year  or  so  after  the  publication  of  the 
Normann  British  and  German  patents  in  1903,  and  that  Kayser's  work,  before 
coming  to  this  country,  was  at  Joseph  Crosfield  &  Sons,  Limited,  of  Warrington, 
England.  D.  R.  11,  Q57-59;  28,  Q191;  64,  Q449,  207;  and  211,  Q9.  Cros- 
fields  were  naturally  much  put  out  about  Kayser  leaving  them  and  coming  to  this 
country,  D.  R.,  154,  Q164,  since,  as  Kayser  states  in  his  letter  of  October  18th, 
he  alone  was  thoroughly  acquainted  with  the  manipulation  of  the  process  which 


662  APPENDIX 

he  had  been  using  for  three  years  and  which  he  proposed  to  introduce  in  this 
country  as  a  process  "  of  the  greatest  possible  importance." 

As  was  to  be  expected,  under  the  circumstances,  Kayser  brought  with  him 
samples  of  the  products  which  he  had  been  producing  at  Crosfield's,  and  it  was 
these  products  which  he  showed  to  Burchenal.  At  least  one  of  these  products 
was  produced  by  hydrogenation  from  cottonseed  oil.  D.  R.,  9-10,  39.  Bur- 
chenal had  no  knowledge  or  interest  in  hydrogenation  prior  to  this  time.  D.  R., 
227-228.  It  is  Burchenal's  assertion  that  the  products  Kayser  brought  with 
him  were  very  hard,  but  the  only  written  record  of  any  of  these  products  is  of  a 
product  "  which  showed  an  iodine  value  of  52.26  and  a  melting  point  of  39.3°  C." 
D.  R.,  122,  last  paragraph.  It  is  indeed  significant  that  the  only  record  of  any 
product  which  Kayser  brought  to  this  country  from  Crosfield's  in  England  had 
a  melting  point  of  39.3°  C.  and  an  iodine  value  of  52.26.  This  product,  which 
Kayser  showed  to  Burchenal,  had  a  melting  point  within  the  range  of  melting 
points  given  in  the  specification  as  filed  of  the  Burchenal  patent  in  suit,  and 
within  the  range  now  given  in  the  patent  in  suit.  The  iodine  value  of  said 
product  is  less  than  3°  lower  than  the  lower  limit  of  iodine  values  of  the  Bur- 
chenal patent  in  suit,  and  far  closer  than  is  the  iodine  value  of  the  defendant's 
product  Kream  Krisp  to  the  upper  limit  of  iodine  values  of  the  patent  in  suit. 
If  one  may  then  judge  from  the  report  of  Dr.  Bender,  Procter  &  Gamble's 
chemist  at  the  time,  and  from  the  records  of  Procter  and  Gamble,  the  only 
samples  from  Crosfield's  which  Kayser  brought  to  this  country  are  the  samples 
having  a  melting  point  and  iodine  value  which  correspond  to  those  of  the 
Burchenal  patent  in  suit.  It  is  evident  that  Burchenal  cannot  claim  that  he  is 
the  inventor  of  any  hydrogenized  oil  or  fat  such  as  that  which  Kayser  brought 
to  this  country  and  showed  to  him. 

After  the  preliminary  negotiations  and  the  building  of  a  small  plant  for  his 
process  at  the  plant  of  Procter  and  Gamble  in  Cincinnati,  Kayser  gave  a  demon- 
stration of  his  process  which  is  described  in  certain  notes  or  reports  which  are 
reproduced  at  pages  120-124  of  the  deposition  record.  These  notes  describe 
the  Kayser  process  in  detail,  as  it  was  disclosed  by  Kayser  to  Burchenal  and  to 
Anderson,  and  as  it  was  practiced  and  demonstrated  by  him.  The  process  is  in 
all  essentials  identical  with  that  described  in  the  Kayser  patents  Nos.  1,004,035 
and  1,008,474  above  referred  to.  In  demonstrating  his  process  Kayser  produced 
products  of  varying  degrees  of  hardness,  as  indicated  by  the  following  melting- 
points:  55.5°  C.;  60.3°  C.;  55°  C.;  60°  C.;  42°  C.;  43°  C.;  59.8°  C. 

The  apparatus  which  was  built  for  Kayser,  and  in  which  he  demonstrated 
his  process  to  Burchenal,  was  completed  and  operated  in  January,  1908.  D.  R., 
11  Q61;  122,  Q851.  Burchenal  was  quite  familiar  with  the  apparatus  at  the 
time  and  observed  its  operation  at  various  times  in  the  early  part  of  1908. 
D.  R.  90,  Q601-604,  and  he  was  also  familiar  with  the  reports  made  by  Kayser 
to  Anderson: 

Q385.  And  reports  were  made  by  Mr.  Kayser  to  Mr.  Anderson? 
A.  Yes,  sir. 

Q386.  And  it  was  from  Mr.  Anderson  that  you  obtained  your  knowl- 
edge of  the  reports?  A.  Oh,  no;  I  was  in  touch  with  them  daily. 

Burchenal  thus  knew  everything  that  Kayser  was  doing;  and  in  particular 
he  knew  of  the  reports  of  Kayser,  with  which  he  was  in  contact  daily.  Theze 
reports,  which  are  in  evidence,  are  few  in  number.  One  of  them,  that  of  March 


EDIBLE  HYDROGENATED  FATS  663 

5,  1908,  describes  the  hydrogenation  of  cottonseed  oil,  to  given  products  with  a 
melting  point  of  42°  C.  and  43°  C.,  respectively.  D.  R.,  124,  125,  Q853.  An- 
derson, to  whom  these  reports  were  made,  has  testified  that  these  reports  were 
absolutely  true  at  the  time  they  were  made,  D.  R.,  170,  Q100,  and  that  Kayser 
was  left  absolutely  to  his  own  initiative  in  the  carrying  out  of  his  process  and 

every  facility  provided  him. 

*     *     * 

The  Kayser  process,  as  described  in  Kayser's  reports,  and  in  the  Kayser  pat- 
ents, has  been  demonstrated  by  defendant's  witness  Richter  in  the  presence  of 
counsel  and  experts  for  the  plaintiff.  The  catalyzer  was  conceded  to  have  been 
produced  in  accordance  with  the  process  used  by  Kayser,  T.  R.,  591,  and  the 
apparatus  and  conditions  of  operation  used  were  those  of  the  Kayser  reports  and 
the  Kayser  patents.  These  experiments  are  described  by  Richter,  and  the  pro- 
priety of  the  procedure  or  the  apparatus  was  not  questioned  on  cross  examina- 
tion. The  oil  used  was  refined  cottonseed  oil,  the  same  as  Kayser  used  in  the 
demonstration  of  his  process  to  Burchenal  early  in  1908.  The  reaction  was 
noted  as  being  a  gradual  and  progressive  reaction  and  the  oil  was  gradually 
increased  in  hardness  as  the  reaction  proceeded.  T.  R.,  608,  Qs225-226.  This 
was  in  fact  to  be  expected  from  the  very  nature  of  the  process,  which  involves 
the  bringing  of  films  or  a  spray  of  the  oil  and  catalyst  progressively  into  an 
overlying  body  of  hydrogen  in  order  that  the  necessary  contact  between  the 
hydrogen,  catalyst  and  oil  may  take  place  and  in  order  that  the  reaction  may 
proceed.  Samples  were  taken  from  time  to  time  during  the  progress  of  the 
process  and  these  samples  which  have  been  produced  in  evidence  show  clearly 
the  gradual  and  progressive  nature  of  the  reaction.  As  with  the  series  of  sam- 
ples produced  by  Dr.  Walker,  Ex.  M,  so  the  series  of  samples  produced  by  Rich- 
ter by  the  Kayser  process  show  a  gradual  and  progressive  hardening  or  satura- 
tion and  a  gradually  increasing  melting  point.  The  two  experiments  demon- 
strating the  Kayser  process  were  called  respectively  the  "  K-run  "  and  the  "  L- 
run."  The  series  of  samples  are  marked  respectively:  K-0,  K-l,  K-2,  &c., 
and  L-0,  L-l,  L-2,  &c.  The  L-run  was  for  the  purpose  of  producing  the  products 
of  melting  point  of  42°  C.  and  43°  C.,  respectively,  which  Kayser  produced  and 
showed  to  Burchenal  on  March  5,  1908.  These  various  samples  and  their 
melting  points,  as  well  as  the  time  required  for  their  production,  are  shown  in 
the  following  table: 

K-  AND  L-RUNS  (KAYSER  PROCESS). 

No.  of  Sample.  Time.  Melting  Point. 

K-0  0  liquid  (cottonseed  oil) 

K-l  17  min.  liquid 

K-2  27     "  liquid 

K-3  37     "  90.5°  F.     32.5°  C. 

K-4  42    "  92.5  33.6 

K-5  57    "  95.4  35.2 

K-6  72    "  101.2  38.4 

K-7  77    "  100.5  38. 

K-8  123     "  106.  41.1 

K-9  303     "  115.8  52.3 

K-10  480     "  121.0  46.5 

K-ll  715    "  126.2  49.4 


664  APPENDIX 

No.  of  Sample.        Time.  Melting  Point. 

L-0                 0  liquid  (cottonseed  oil) 

L-l                 1  hr.  liquid 

L-2                2  "  97.5  36.4°  C. 

L-3                 3  "  103.0  39.4 

L-4  3£  "  106.0  41,2 

L-5  3f  "  106.8  41.8 

L-6                3  hr.  50  min.  107.8  42.1 

L-7                4  hr.  5  min.  108.9  42.8 


The  products  designated  L-6  and  L-7  are  the  products  which  correspond, 
within  a  small  fraction  of  a  degree,  to  the  products  of  melting  point  42°  C.  and 
43°  C.,  which  Kayser  produced  and  showed  to  Burchenal  on  March  5,  1908, 
D.  R.,  124,  as  above  pointed  out.  The  iodine  values  of  these  two  products 
L-6  and  L-7  are  respectively  55.4  and  54.5,  which  correspond  to  the  iodine 
value  55  found  as  the  lower  limit  of  iodine  values  in  the  Burchenal  patent  in 
suit.  These  two  products  L-6  and  L-7  therefore  have  the  same  melting  points 
and  iodine  values  as  the  product  of  the  patent  in  suit,  as  such  product  was 
defined  in  the  application  when  filed,  since  this  application  as  filed  gave  no  other 
directions  for  producing  the  product  than  to  stop  when  the  product  had  a  melting 
point  of  36  to  43°  C.;  and  such  products  were  stated  to  have  an  iodine  value  of 
55  to  80.  Nevertheless,  and  even  though  these  samples  L-6  and  L-7  corre- 
spond in  melting  point  and  iodine  value  with  the  products  of  the  Burchenal 
application  as  filed,  their  composition,  as  indicated  by  their  content  of  saturated 
glycerides,  olein  and  linolin,  is  quite  different  from  that  introduced  into  the 
Burchenal  application  by  amendment  and  now  found  in  the  Burchenal  patent, 
as  will  appear  from  the  following  comparison. 

Burchenal  Patent 

L-6.  L-7. 

Melting  point  (application  as  filed) 36-43  42 . 1  43 . 1 

Iodine  value 55-80  55 . 4  54 . 5 

Saturated  glycerides 20-25%  39 . 9  40 . 5 

Olein 65-75%  56.2  55.6 

Linolin 5-10%  3.9  3.9 

The  composition  of  these  two  products,  L-6  and  L-7,  is  shown  on  triangular 
chart  403.  D.  R.,  609.  It  may  be  here  noted,  as  is  pointed  out  elsewhere  in 
the  brief,  that  the  Kayser  process  followed  in  producing  these  products  L-6  and 
L-7  is  the  same  process  described  in  the  Burchenal  patent  in  suit,  and  that  the 
Burchenal  patent  gives  no  other  directions  for  the  production  of  a  product 
having  the  composition  specified  in  the  patent  than  those  which  were  followed 
in  the  production  of  L-6  and  L-7.  The  semi-solid  product  of  the  patent,  there- 
fore, cannot  be  produced  without  experimentation  and  without  ascertaining  the 
necessary  conditions  for  its  production;  and  the  product  having  the  composi- 
tion stated  in  the  patent  is  not  accordingly  the  product  originally  described  and 
having  the  melting  point  and  iodine  value  originally  stated. 

The  samples  Lr-6  and  L-7  are  edible,  T.  R.  592,  Q134;  611,  XQ259;  and 
Richter  has  testified  that  he  has  made  many  products  by  the  same  process  and 


EDIBLE  HYDROGENATED  FATS  665 

of  a  similar  nature  and  that  they  all  proved  edible.  T.  R.  611,  XQ263.  Upon 
aeration  of  these  products  L-6  and  L-7,  by  laboratory  methods,  to  approximate 
those  in  which  lard  and  lard  substitutes  are  aerated  by  passing  over  the  chilling 
rolls  and  aerating  with  pickers,  these  products  are  converted  into  a  "  salve-like 
product "  of  lard  consistency  as  appears  from  Exhibits  C-l  and  D-l,  and 
from  Richter's  testimony. 

The  product  L-3  has  a  melting  point  of  39.4,  which  is  almost  identical  with 
the  product  of  melting  point  39.3  which  Kayser  brought  to  this  country  from 
Crosfield's  and  showed  to  Burchenal.  This  product  is  even  softer  in  consistency 
than  the  samples  L-6  and  L-7,  as  is  to  be  expected  from  its  lower  melting  point. 
The  samples  K-6  and  K-7  are  also  of  a  like  melting  point  to  that  of  the  product 
which  Kayser  brought  to  this  country  and  showed  to  Burchenal  as  one  of  the 
products  (and  the  only  product  so  far  as  the  records  of  Procter  and  Gamble 
show)  of  the  process  which  he  desired  to  exploit  in  this  country  and  which  he 
represented  to  Procter  and  Gamble  as  a  process  as  "of  the  greatest  possible 
importance." 

The  history  of  hydrogenation  at  Procter  and  Gamble's  will  be  dealt  with  more 
in  detail  in  a  subsequent  portion  of  the  brief;  and  it  will  be  shown  that  edible 
hydrogenized  cottonseed  oil  was  used  in  making  lard  substitutes  and  that  such 
lard  substitutes  were  sold  in  large  quantities  by  Procter  and  Gamble  long  before 
the  alleged  invention  by  Burchenal  of  the  food  product  of  the  patent  in  suit; 
so  that  such  lard  substitutes  are  also  a  part  of  the  prior  art  so  far  as  the  Bur- 
chenal patent  in  suit  is  concerned.  In  the  present  discussion  of  the  Kayser 
process,  as  a  part  of  the  prior  art,  we  have  shown  that  the  Kayser  process,  as 
well  as  the  batch  processes  of  Normann,  Fokin,  and  Paal  and  Roth,  is  a  grad- 
ual and  progressive  process  and  a  process  which  inevitably  and  of  necessity  gives 
all  the  intermediate  products  between  the  original  oil  and  the  final  and  ultimate 
degree  of  saturation  which  may  be  aimed  at.  We  have  also  shown,  by  pro- 
ducing the  products  which  Kayser  brought  to  this  country  and  showed  to 
Burchenal,  and  which  Kayser  produced  on  March  5,  1908,  and  showed  to  Bur- 
chenal, that  they  were  edible  products,  as  Burchenal  in  fact  concedes,  and  that 
these  products  correspond  to  the  product  of  the  Burchenal  application,  as  filed, 
of  the  patent  in  suit.  In  Kayser's  actual  demonstration  of  the  process  in  1908, 
as  Burchenal  has  testified,  samples  were  taken  from  time  to  time,  just  as  sam- 
ples were  taken  from  time  to  time  in  the  K-  and  L-runs  above  referred  to.  Bur- 
chenal in  fact  states  that  the  taking  of  samples  from  time  to  time  was  the  reg- 
ular procedure  in  experimental  work.  D.  R.  17,  QslOO-101.  Burchenal  also 
appreciated  that  the  Kayser  process  was  a  progressive  reaction  during  which  the 
hydrogen  was  gradually  absorbed,  the  oil  gradually  hardened,  the  iodine  value 
gradually  decreased,  and  the  solidification  point  gradually  raised.  D.  R.  21, 
Qsl33-136.  Anderson  has  similarly  testified  that  the  Kayser  process  is  a  grad- 
ual process  and  a  progressive  reaction,  the  oil  gradually  changing  from  a  liquid 
to  a  semi-liqudi  consistency  and  then  to  a  relatively  hard  consistency. 


Kayser  had  been  manipulating  his  process  for  three  years  before  he  came  to 
this  country  and  he  himself  stated  in  his  letter,  D.  R.,  page  207,  that  he  was 
thoroughly  familiar  with  it.  He  brought  to  this  country  samples  of  a  melting 
point  of  39.3°  as  representing  the  products  produced  by  his  process;  and  on  the 
basis  of  these  samples,  and  perhaps  others  of  which  there  is  no  analytical  record, 


666  APPENDIX 

he  induced  Procter  and  Gamble  to  sidetrack  other  work  in  order  to  give  him  the 
right  of  way  to  demonstrate  his  process  by  which  such  products  could  be  pro- 
duced. 

*  *     * 

The  only  oil  particularly  referred  to  in  the  Kayser  patents  is  cottonseed  oil; 
and  the  evidence  shows  that  this  is  the  only  oil  that  he  hydrogenized  in  his 
early  work  in  this  country,  as  well  as  one  of  the  oils  which  he  hydrogenized  and 
brought  to  this  country  with  him.  It  was  moreover  refined  cottonseed  oil  that 
Kayser  used  in  all  his  work  after  coming  to  this  country  in  1908.  D.  R.,  167, 

Qs69-73. 

*  *     * 

Kayser  finally  concluded  his  work  in  this  country  and  returned  to  England. 
He  is  now  a  stockholder  in  the  Procter  and  Gamble  Company.  D.  R.,  51, 
Q376.  The  defendant  in  this  case,  misled  into  believing  that  Kayser  was  no 
bnger  in  the  employ  of  the  Procter  and  Gamble  Company  or  subject  to  its 
control,  T.  R.,  639,  went  to  great  expense  and  trouble  in  an  attempt  to  find 
Kayser  and  find  out  from  him  about  his  work  in  this  country;  and  a  repre- 
sentative was  sent  to  England  in  war  time  to  interview  Kayser,  only  to  find, 
after  long  delay  and  much  difficulty,  that  Kayser's  mouth  was  closed.  We  now 
know  that  Kayser  has  been  in  the  employ  of  Procter  and  Gamble  continually 
and  that  he  is  under  agreement  with  them  not  to  disclose  any  information 
regarding  anything  he  did  while  in  their  employ.  Similarly  an  attempt  was  made 
to  find  out  from  Crosfields  about  the  work  which  Kayser  did  before  coming  to 
this  country.  But  Crosfields'  mouth  was  also  closed.  We  now  know  that  the 
relations  of  Crosfields  with  the  Procter  and  Gamble  Company  are  such  that, 
in  the  language  of  Burchenal: 

We  would  consider  it  a  breach  of  faith  if  they  (Crosfields)  disclosed  any 
information  regarding  the  hydrogenation  of  fats,  to  the  competitors  of  the  Procter 
and  Gamble  Company. 

The  only  information,  therefore,  which  we  have  about  Kayser's  work  in  this 
country  and  his  relations  with  Burchenal,  is  the  oral  testimony  of  officials  of  the 
plaintiff  company  and  the  reports  of  Kayser's  work  which  are  in  evidence;  and 
the  testimony  of  Kayser's  friend  and  only  confidant,  Clarence  von  Phul. 

After  Kayser  had  completed  his  work  in  this  country  and  had  returned  to 
Europe;  after  he  had  demonstrated  his  process,  had  produced  his  products, 
and  had  made  his  final  contract;  after  he  had  been  made  a  stockholder  in  the 
Procter  and  Gamble  Company;  and  after  Crosfield  had  in  1909  been  paid  a 
large  sum  of  money  for  their  rights  in  this  country,  D.  R.,  153-155,  Kayser  left 
this  country  in  July  of  1910.  D.  R.,  116;  Q818.  After  Kayser  was  thus  out 
of  the  way,  and  had  been  placed  under  contract  not  to  disclose  anything  he 
did  in  this  country;  then,  and  only  then,  did  Burchenal,  in  November,  1910, 
file  the  application  of  the  patent  in  suit  and  claim  the  semi-solid  product  of 
Kayser's  process  as  his  (Burchenal's)  invention. 

It  will  possibly  be  urged  on  behalf  of  plaintiff  that  the  semi-solid  products 
which  Kayser  made  on  March  5,  1908,  of  a  melting  point  of  42  and  43°  C., 
were  not  produced  intentionally  and  were  not  considered  to  have  any  value. 
But  such  a  contention  is  of  no  persuasive  force,  inasmuch  as  among  the  products 
which  Kayser  brought  with  him  to  this  country  and  showed  to  Burchenal,  was 


EDIBLE  HYDROGENATED  FATS  667 

one  shown  by  Procter  and  Gamble's  own  records  as  having  a  melting  point  of 
39.3°  C.,  exhibited  by  him,  with  the  others,  as  products  produced  by  his  process, 
which  he  had  represented  as  "  of  the  greatest  possible  importance."  In  respect 
of  the  products  of  a  melting  point  of  42  and  43°  C.,  produced  by  Kayser  on 
March  5,  1908,  these  products  were  produced  by  Kayser  and  shown  to  Burchcnal 
and  Anderson,  and  Anderson's  report  describing  these  products  and  their  melting 
points  was  considered  of  such  value  that  it  was  kept  as  one  of  the  very  few 
reports  of  the  work  which  Kayser  did. 


PLAINTIFF'S  CONTENTION  AS  TO  PRIOR  ART  UNTENABLE 
1.  Utility. 

Dr.  Baskerville  contends  that  any  product  of  a  degree  of  hydrogenation  short 
of  substantial  completion  is  not  described  or  suggested  in  the  prior  art  as  having 
any  utility  whatsoever.  T.  R.,  page  758,  Q190.  He  does  not  contend  that  the 
completely  hydrogenized  products  were  not  recognized  as  having  utility.  He 
assumes  on  the  contrary  that  these  products  were  for  use  in  making  soap  or 
candles.  T.  R.,  page  750,  Q182.  If  he  concedes  that  oil  technologists,  or 
those  skilled  in  the  fat  and  oil  industry,  had  sufficient  information  to  employ 
the  hydrogenated  products  in  the  manufacture  of  soap  and  candles  by  exercising 
the  skill  of  their  calling,  he  is  illogical  in  not  further  conceding  that  in  the 
exercise  of  that  same  skill  they  recognized  the  utility  of  the  hydrogenated  fats  in 
the  production  of  food  products. 

But  it  cannot  be  of  importance  whether  the  investigators  of  the  prior  art 
actually  described,  or  even  knew  of,  all  the  uses  to  which  their  products  could 
be  put,  for,  as  a  matter  of  law,  they  are  entitled  to  all  the  uses  thereof  whether 
they  described  or  conceived  of  such  use  or  not,  as  has  uniformly  been  held  by 

the  courts. 

*  *     * 

It  follows,  as  a  conclusion  of  law,  that  Normann,  Fokin,  Bedford  and  Williams, 
Paal  and  Roth,  Erdmann  and  Kayser,  were  entitled  to  use  their  respective 
products,  in  any  of  the  various  degrees  of  hydrogenation  in  which  they  might 
be  produced,  for  any  of  the  uses  for  which  they  were  adapted,  whether  they 
described  or  conceived  of  all  of  such  uses  or  not. 

And  just  as  inventors  are  entitled  to  all  the  uses  of  their  inventions  whether 
they  had  conceived  of  or  described  such  uses  or  not,  so  the  public  is  entitled  to 
all  the  uses  of  things  which  are  public  property. 

*  *     * 

It  logically  follows  that  Burchenal  could  not  patent  the  old  hydrogenized  fats 
of  the  prior  art,  as  food  products,  merely  because  he  was  the  first  to  describe 
their  use  for  that  purpose;  for,  under  the  decisions  above  cited,  the  new  use  of 
and  old  thing  does  not  make  the  thing  itself  patentable,  even  if  such  use  had 
not  been  proposed  before.  And  this  would  be  true  even  if  the  old  products 
were  not  known  to  be  edible,  or  were  even  considered  inedible. 

*     *     * 

The  hydrogenized  products  of  the  prior  art  are,  in  fact,  edible,  and  this  is  not 
denied,  but  conceded. 


668  APPENDIX 

And  yet  Dr.  Baskerville  stakes  the  plaintiff's  whole  case  upon  the  alleged  dis- 
covery 

that  the  partially  hydrogenated  oil  itself  could  be  used  directly  as  a  food. 
T.  R.,  757. 

II.  Degree  of  Hydrogenation  or  Saturation. 

Dr.  Baskerville  contends  that  the  aim  and  object  of  the  investigators  of  the 
prior  art  was  complete  saturation;  that  the  idea  of  partial  saturation  seems  to 
him  to  have  been  incidental;  and  that  the  stopping  of  the  process  to  give  a 
semi-solid  product  was  not  taught  in  the  prior  art.  T.  R.,  758.  Yet  the  pro- 
cesses of  Normann,  Fokin,  Paal  and  Roth  and  Kayser,  were  all  of  a  gradual 
and  progressive  nature,  and  were  so  recognized  and  described;  and,  as  a  neces- 
sary step  in  carrying  out  such  processes,  all  the  various  intermediate  degrees  of 
partial  hydrogenation  were  obtained.  Fokin,  Paal  and  Roth  and  Kayser  all 
point  out  how  the  reaction  can  be  followed  step  by  step,  and  Kayser  specifically 
states  that  semi-solid  products  are  obtained  if  desired.  Dr.  Baskerville  cannot, 
in  the  face  of  these  prior  disclosures,  be  heard  to  deny  that  semi-solid  and  in- 
completely hydrogenized  oils  of  different  consistencies  were,  in  fact,  produced  and 
described.  Apparently  Dr.  Baskerville  did  not  know  that  the  product  Kayser 
brought  to  this  country  and  showed  to  Burchenal  as  the  product  of  a  process 
"  of  the  greatest  possible  importance  "  was  a  semi-solid  of  melting  point  39.3°  C. 
and  iodine  value  52.26,  and  he  did  not  recall  the  teaching  of  the  Kayser  patents. 

*  *     * 

That  it  is  an  obvious  thing  to  stop  the  hydrogenation  half  way,  or  at  any 
other  intermediate  point,  instead  of  carrying  it  to  completion,  and  that  anyone 
would  naturally  know,  and  as  a  matter  of  course  did  know,  that  this  could  be 
done,  without  knowledge  of  the  patent  in  suit,  and  without  invention,  is  indicated 
(in  addition  to  Kayser's  disclosures)  by  the  following  excerpt  from  the  British 
patent  to  Paal  No.  5188  of  1911,  which  counsel  for  plaintiff  was  the  first  to 
quote  as  interpretive  of  the  prior  art  and  which  was  published  long  prior  to  the 
grant  of  the  patent  in  suit. 

The  reduction  process  may  also,  of  course,  be  carried  on  in  such  a 
manner  that  only  partial  reduction  ensues.  These  partially  reduced 
fats  then  exhibit  a  lowered  melting  point  and  a  consistency  resembling 
ointment. 

The  degree  of  hydrogenation  can  be  determined  by  ascertaining  the 
iodine  value.  (Italics  ours.) 

*  *    * 

An  unprejudiced  view  of  the  hydrogenation  of  oils  for  food  purposes  is  found 
in  Bulletin  469  of  the  Dept.  of  Agriculture,  entitled  "Fats  and  Their  Economic 
Use  in  the  Home  "  by  Holmes  and  Lang,  Scientific  Assistants,  Office  of  Home 
Economics,  published  Dec.  15,  1916.  This  Government  publication  was  first 
quoted  by  Dr.  Baskerville  as  an  authority,  T.  R.,  746,  and  was  introduced  in 
evidence  by  the  defendant  as  Exhibit  P2.  Defendant's  Ex.  Book,  pages  151- 
177. 

The  following  is  found  on  pages  14  and  15.     Ex.  Book,  pages  164-165. 

Hardened  vegetable  oils,  technically  known  as  hydrogenated  oils,  which 
have  much  the  same  consistency  as  lard  or  butter,  have  been  put  on  the 


EDIBLE  HYDROGENATED  FATS  669 

market  within  recent  years.  They  are  commercial  possibilities  owing  to 
the  fact  that  as  a  result  of  a  long  series  of  laboratory  experiments,  processes 
have  been  discovered  by  which  oils  may  be  transformed  into  a  product  of 
any  desired  hardness  by  chemically  adding  hydrogen  to  them.  This 
reaction  takes  place,  for  instance,  when  finely-divided  nickel  hydrogen 
and  the  oil  to  be  hardened  are  intimately  mixed  under  proper  conditions. 
The  nickel  does  not  enter  into  the  composition  of  the  hardened  fat, 
but  is  removed  and  used  repeatedly  in  the  preparation  of  other  batches. 
The  hardened  oils  are  generally  white  in  color,  have  no  appreciable  odor 
or  taste,  and  are  less  likely  to  become  rancid  than  the  original  oil.  (Italics 
ours.) 

Burchenal  made  no  "  laboratory  experiments  "  and  "  discovered  "  no  "  proc- 
esses "  which  resulted  .in  such  "  commercial  possibilities."  Normann,  Fokin, 
Bedford,  Paal  and  Roth  made  the  experiments  and  discovered  the  processes,  and 
published  these  to  the  world.  Burchenal  has  done  nothing  to  "  advance  the 
progress  of  science  and  of  the  useful  arts  "  that  would  entitle  him  to  take  away 
from  these  prior  experimenters  and  discoverers  the  fruits  of  their  labors,  and 
from  the  public  its  birthright.  Yet  to  permit  his  patent  to  stand  would  be  to 
deny  Normann  and  the  other  prior  investigators  and  patentees  the  right  to  put 
to  the  chief  use  of  fats — that  as  food — their  hydrogenated  products,  in  the 
various  degrees  of  saturation  which  they  describe. 


III.  Use  of  Hydrogenized  Fats  for  Food. 

Dr.  Baskerville  argues  that  the  teaching  of  the  prior  art  repels  rather  than 
suggests  the  use  of  hydrogenized  oil  for  culinary  purposes.  In  support  of  his 
contention,  he  gives  his  reasons  which  may  be  briefly  condensed  and  discussed 
as  follows: 

1.  He  suggests,  by  inference,  that  the  hydrogenized  oils  were  to  be  used  for 
candles  and  soaps.     Q182,  T.  R.,  p.  750.     Why  he  picked  out  these  two  products 
to  the  exclusion  of  food  products  is  not  apparent,  because  the  prior  art  patents 
and  publications  describe  specifically  no  special  uses  for  the  hydrogenized  prod- 
ucts.    It  would  have  been  as  superfluous  for  the  earlier  patentees  and  investi- 
tigators  of  hydrogenized  fats  to  suggest  the  common  and  ordinary  uses  of  the 
fats,  as  it  would  have  been  for  the  originator  of  aniline  by  a  new  process  to  say 
it  could  be  used  for  dyes,  or  of  the  originator  of  synthetic  sugar  to  say  that  it 
could  be  used  as  a  sweetening  for  food.     And  it  is  conceded  by  Dr.  Baskerville, 
and  by  counsel  for  plaintiff,  as  it  must  be  conceded,  that  the  products  of  the 
prior  art  were  in  fact  edible,  whatever  their  degree  of  hydrogenation.     T.  R.,  676. 

2.  He  says  that  Normann's  statement  hi  his  British  patent  No.  1515  of  1903 
that  there  were  no  secondary  reactions  in  hydrogenation  "  apart  from  the  forma- 
tion of  small  quantities  of  nickel  soap  which  may  be  easily  removed  by  dilute 
mineral   acids "    indicates   that   the   product   is   something   which   is   not   to   be 
regarded  as  suitable  for  food. 

Dr.  Bacon  has  logically  pointed  out  that  Normann  told  how  to  remove  those 
nickel  soaps  which  might  have  prevented  such  use,  thus  indicating  to  any  skilled 
chemist,  in  terms  which  a  chemist  would  understand,  that  the  product  was 
edible. 


670  APPENDIX 

3. -Dr.  Baskerville  quoted  Paal  and  Roth,  who  had  discovered  in  the  course 
of  their  physiological  investigations  that  hydrogenation  changed  an  inedible  or 
poisonous  croton  oil  into  an  edible  or  non-poisonous  tallow.  To  anybody  but 
Dr.  Baskerville,  this  would  indicate  that  Paal  and  Roth,  by  their  physiological 
investigations,  of  course  knew  that  the  usual  food  oils  were  edible  when  hydro- 
genized,  and  commented  only  on  what  was  really  a  discovery,  to  wit,  that  poi- 
sonous croton  oil  became  non-poisonous  on  hydrogenation.  He  quoted  their 
statement  that  they  studied  the  partially  and  completely  hydrogenized  oil,  and 
their  statement  that  cottonseed  oil  when  hydrogenized  gave  a  negative  Hal- 
phen  test.  The  several  quotations  Dr.  Baskerville  gave  from  Paal  and  Roth's 
article  show  that  they  said  they  employed  the  tests  "  used  in  food  chemistry." 
It  seems  to  us  that  the  significance  of  that  statement  has  entirely  escaped  Dr. 
Baskerville  as  well  as  their  statement  that  they  studied  the  partially  hydrogenized 
oil. 

*     *    * 

5.  He  summarizes  his  conclusions  as  follows: 

So  it  appears  to  me  that  Burchenal  really  made  a  seedless  prune,  as 
you  may  put  it,  or  spineless  cactus.  He  Burbanked  the  oils,  as  you  might 
put  it.  And  by  his  work  he  actually  made  two  discoveries:  first,  that 
the  hydrogenated  oil  could  be  put  into  a  compound  and  used  as  a  food; 
and,  second,  that  the  partially  hydrogenized  oil  itself  could  be  used 
directly  as  a  food,  and  thus  he  founded  what  is  known  as  the  hydro- 
genized food  industry.  (Italics  ours.) 


Burchenal  says  that  neither  he  nor  anyone  on  his  behalf  made  any  tests  of 
hydrogenized  oils  for  cooking  or  edible  purposes  before  Flake  White  containing 
hydrogenized  fat  was  put  on  the  market  and  sold.  On  the  contrary,  Burchenal 
claims  that  he  merely  used  his  perceptive  faculties,  or,  as  he  put  it,  arrived  at  a 
conclusion  that  Kayser's  hydrogenized  oil  was  edible — by  a  process  of  "  cere- 
bration." But  even  if  one  should  have  made  some  experiments  to  see  whether 
the  hydrogenized  fats  were  edible,  would  that  have  required  the  exercise  of  the 
inventive  faculty?  Dr.  Baskerville  says,  in  effect,  that  it  would  have  been  the 
normal  every  day  work  of  a  food  or  oil  chemist,  for  first  he  concedes  that  the 
greatest  use  of  fats  and  oils  of  animal  and  vegetable  origin  is  for  foods,  and  then 
he  concedes  that  if  an  oil  or  fat  unknown  to  him  had  been  presented  to  him,  he 
would  have  used  the  expected  skill  of  his  calling  and  ascertained  its  technological 
uses  by  casting  "  around  to  see  the  uses  that  fats  were  put  to."  T.  R.,  772; 
XQ282-286.  Probably  he  would  not  have  been  so  sapient  as  Burchenal  claims 
to  have  been  in  arriving  at  a  conclusion  that  hydrogenized  fats  were  edible, 
merely  by  a  process  of  cerebration,  and  would  have  eaten  some  of  the  fat  or 
cooked  with  it,  but  that  would  have  been  only  the  ordinary  use  to  which  fats 
are  put.  Yet  surely  this  cannot  be  considered  an  exercise  of  the  inventive 

faculties. 

*     *     * 

Dr.  Baskerville  would  have  cast  about  to  see  what  use  fats  were  put  to. 
Can  he  imagine  that  Normann,  or  Fokin,  or  Paal  and  Roth  did  not  do  that? 
They  were  scientific  men.  They  did  not  state  the  obvious.  Paal  and  Roth 
announced  what  was  not  obvious,  to  wit,  that  poisonous  croton  oil  was  ren- 


EDIBLE  HYDROGENATED  FATS  671 

dered  non-poisonous;  and  if  they  had  thought  that  edible  oils  when  hydro- 
genized were  rendered  inedible  or  poisonous,  it  is  unthinkable  that  they  would 
not  have  said  so. 

It  is  apparent  then  that  Dr.  Baskerville's  conclusions  are  untenable.  Bur- 
enal's  Burbanked  "  seedless  prune "  and  "  spineless  cactus "  on  closer  inspec- 
tion are  found  after  all  to  be  only  plants  of  the  common  garden  variety. 

Dr.  Baskerville  paid  his  tribute  to  the  wrong  person.  It  was  Normann  who 
"  Burbanked  the  oils." 

*     *     * 

From  whatever  aspect  this  case  be  viewed,  when  the  discovery  that  oils  and  fats 
may  be  hydrogenized  into  solids  or  semi-solids  (and  thereby  be  availed  of  in  such 
form  as  lard  substitutes)  is  considered,  it  is  to  Normann  "  that  the  honor  of  this 
discovery  belongs."  It  does  not  belong  to  this  country  or  to  Burchenal. 

FURTHER  DETAILS  OF  EARLY  HYDROGENATION  WORK  AT  PROCTER  &  GAMBLE'S 

Reference  has  already  been  made  herein  to  the  Kayser  patents  1,004,035  and 
1,008,474,  which  were  cited  as  references  by  the  Examiner  against  the  claims  of 
the  patent  in  suit,  and  which  are  admitted  by  Burchenal  as  part  of  the  prior  art. 

The  defendant,  under  order  of  the  Court,  took  the  depositions  of  Burchenal, 
Anderson,  McCaw  and  Morrison,  all  officers  of  the  plaintiff  company,  in  refer- 
ence to  the  Kayser  process  of  hydrogenizing  oils. 

The  following  facts,  briefly  hereinbefore  referred  to,  were  developed: 

Edwin  Cuno  Kayser  had  for  some  years  been  in  the  employ  of  Crosfield  & 
Sons,  Ltd.,  an  English  firm,  which  with  Dr.  Normann,  D.  R.,  page  76,  Q518, 
had  been  developing  improved  procedures  in  the  hydrogenation  of  oils.  On 
October  18th,  1907,  Kayser  wrote  to  the  plaintiff,  whose  main  business  was 
then  and  is  now  the  manufacture  of  soap,  stating  that  he  proposed  visiting  the 
United  States  for  the  purpose  of  introducing  "  a  process  of  the  greatest  possible 
importance  to  soap  manufacturers,"  that  he  had  manipulated  the  process  for 
three  years,  and  was  "  the  only  person  thoroughly  acquainted  therewith." 

After  a  brief  correspondence,  Kayser  arrived  in  this  country  in  November, 
1907,  and  called  on  Burchenal,  bringing  with  him  samples  of  hydrogenized  oils 
including  hydrogenized  cottonseed  oil  and  hydrogenized  maize  (corn)  oil  and 
showed  them  to  Burchenal.  Burchenal  had  never  before  seen  or  heard  of  hydro- 
genized oils,  and  was  not  even  familiar  with  lard  compounds.  The  samples 
brought  by  Kayser  were  "  very  light  hi  color,  pale  yellow  or  almost  white." 
After  certain  negotiations,  a  preliminary  contract  was  made  with  Kayser  on 
Dec.  5,  1907,  and  Kayser  then  told  Burchenal  that  the  samples  referred  to  had 
been  produced  by  hydrogenating  cotton  seed  oil  in  the  presence  of  a  catalyst. 

Kayser  was  very  secretive  and  mysterious  and  evidently  disinclined  to  tell 
anything  more  than  he  had  to.  Burchenal  says  "  There  was  a  good  deal  of 
mystery  about  Mr.  Kayser."  There  is,  however,  a  written  record  giving  a 
qualitative  analysis  of  one  of  Kayser's  samples  brought  from  Crosfield  &  Sons, 
showing  that  it  was  a  semi-solid,  with  "  an  iodine  value  of  52.26  and  a  melting 
point  of  39.3°  C.;"  so  that  the  first  hydrogenized  oil  which  Burchenal  ever  saw 
was  a  "  white  or  yellowish  semi-solid  "  with  a  melting  point  within  the  range  of 
36°-43°,  the  range  which  Burchenal  specified,  when  he  filed  his  application  for 
the  patent  in  suit,  as  the  melting  point  range  of  his  product  and  within  the 
melting  point  range  of  33  to  40°  specified  in  the  patent  itself. 


672  APPENDIX 

Burchenal  says  now  that  Kayser's  samples  were  hard,  but  the  report  is  clear 
as  to  the  melting  point,  and  is  more  to  be  relied  on  than  Burchenal's  assertion 
or  memory. 

Burchenal  was  forced — unwillingly  it  is  true,  to  concede  that  those  samples 
which  Kayser  had  brought  from  England  were  edible. 

Q393.  But  was  there  anything  inherent  to  this  product  which  he 
brought  with  him,  which  rendered  it  inedible? 

A.  Nothing,  I  should  think,  except  the  fact  that  the  idea  of  edibility 
had  not  been  associated  with  it.  (Italics  ours.) 

During  December,  1907,  and  the  early  part  of  January,  1908,  a  small  experi- 
mental plant  was  built  under  Kayser's  directions  at  the  plaintiff's  factory,  includ- 
ing a  hydrogenating  apparatus  like  that  shown  on  sheet  1  of  the  drawings  of 
the  Kayser  patent  1,004,035,  and  capable  of  hydrogenizing  a  batch  of  20  pounds 
of  oil.  D.  R.,  pages  160-165.  The  process  and  the  apparatus  were  disclosed  in 
detail  to  Burchenal  and  Anderson,  and  also  the  precise  method  of  making  tke 
nickel-kieselguhr  catalyst.  On  January  17th,  1908,  Kayser  alone  hydrogenized 
refined  summer  yellow  cotton-seed  oil  in  his  apparatus  and  produced  hardened 
fats  of  melting  points  of  55.5°  C.  and  60.3°  C.  D.  R.,  122-123.  Five  days 
later  on  January  22,  1908,  in  the  presence  of  Anderson,  Kayser  hydrogenized  a 
second  batch  of  the  same  oil,  and  during  the  month  of  January,  1908,  there  was 
prepared  by  Anderson,  under  Kayser's  directions,  a  complete  description  of  the 
process  of  hydrogenation,  which  appears  on  pages  120  and  121  of  the  Depo- 
sition Record,  and  which  contains  the  following: 

The  process  of  saturation  is  very  interesting.  Hydrogen  is  circulated 
as  taken  up  by  the  fat.  .  .  .  The  affinity  of  the  fat  for  the  hydrogen  is 
plainly  evidenced  in  this  operation.  As  the  saturation  nears  completion, 
less  gas  is,  of  course,  taken  up  by  fat  and  an  excess  is  circulated,  which 
causes  bubbling  at  end  of  the  outlet  tube.  Completion  of  saturation  is 
indicated  by  comparison  of  volume  of  gas  in  and  out  of  machine.  When 
saturation  is  practically  complete,  the  gas  passes  through  without  any 
apparent  reduction  in  volume.  The  fat  is  drawn  out  of  the  machine — a 
black  mass,  on  account  of  presence  of  catalyzer,  and  passes  through  filter 
press,  the  catalyzer  filtering  out  very  rapidly.  The  filtered  fat  is  the  fin- 
ished product. 

There  were  in  addition  three  other  written  reports,  dated  respectively  Feb.  6, 
1908,  March  5,  1908,  and  May  7,  1908,  all  printed  in  the  Deposition  Record  on 
page  124,  showing  work  done  by  Kayser  in  the  hydrogenation  or  treatment  of 
oil.  The  first  shows  a  mixture  of  hydrogenized  oil  and  "prime  tallow";  the 
second,  two  batches  of  semi-solid  hydrogenized  oil,  one  having  a  melting  point 
of  42°  C.  and  the  other  having  a  melting  point  of  43°  C.;  and  the  third  showing 
the  melting  point  of  the  fat  acids  of  a  large  batch  of  hydrogenized  oil  sent  to 
McCaw  at  Macon,  Ga.  (These  fats  of  42°  and  43°  C.  melting  point  have  been 
reproduced  by  Richter  as  Exhibits  A'  and  A'  and  have  already  been  discussed.) 

Anderson  says  that  the  cottonseed  oils  treated  by  Kayser  were  all  "  refined 
oils,"  Q74,  D.  R.,  page  167,  and  therefore  edible.  Burchenal  and  Anderson 
were  in  daily  touch  with  the  work  Kayser  was  doing — but  all  the  other  em- 
ployees of  the  plaintiff  were  kept  in  ignorance.  On  this  point  Anderson  testi- 
fied as  follow  (italics  ours): 


EDIBLE  HYDROGENATED  FATS  673 

Q326.  Who  besides  Mr.  Burchenal,  Mr.  Kayser  and  yourself  saw  or 
became  familiar  with  any  of  the  processes  or  products  carried  on  or  pro- 
duced by  Mr.  Kayser  during  1908  and  1909?  A.  Well,  during  1908,  no 
one  but  Mr.  Burchenal  and  myself.  We  occasionally  gave  Mr.  Kayser 
a  laborer  to  help  him,  but  we  changed  the  laborer  every  week.  He  did 
all  the  work  himself  and  no  one  came  in  contact  with  him  but  Mr. 
Burchenal  and  myself. 

Q327.  How  about  1909?  A.  1909,  after  we  started  the  plant,  Mr. 
Leach  was  introduced  into  it. 

Q328.  Since  that  time  the  process —  A.  And  it  has  gradually  broad- 
ened out  since  that  time.  In  the  first  two  years  we  would  arrest  anyone — 
anybody  who  was  seen  talking  to  Kayser,  except  ourselves. 

Q329.  That  same  degree  of  secrecy  has  practically  been  preserved  ever 
since?  A.  Oh,  no;  it  has  broadened  quite  a  lot  beyond  that — quite  a 
few  people  now  know  about  it. 

Q330.  Quite  a  few  people  know  it,  in  order  to  carry  on  the  process? 
A.  In  order  to  carry  on  the  large  volume  of  business,  to  take  care  of  the 
increased  work. 

Q331.  But  the  knowledge  is  confined  to  such  people  as  you  employ? 
A.  Yes. 

Q332.  The  knowledge  is  confined  to  such  people  as  you  employ  in 
making  the  hardened  oil  or  substance?  A.  In  the  beginning  our  labora- 
tory people  did  not  know  anything  about  it,  as  such. 

Q333.  And  you,  up  to  the  present  time,  keep  the  knowledge  from  the 
public  just  as  far  as  it  is  possible  to  do  so?  A.  Just  as  far  as  we  know 
how. 

Anderson  was  asked  whether  the  products  produced  by  Kayser  on  March  5, 
1908,  having  melting  points  of  42°  and  43°  C.  were  edible  as  food  products  and 
he  stated  that  they  were. 

Q235.  And  would  you  also  say  that  a  product  having  a  melting  point 
of  42  degrees  Centigrade  and  produced  by  circulating  hydrogen  gas  through 
cotton-seed  oil,  in  which  nickelized  kieselguhr  is  maintained  in  suspension  by 
agitators  in  the  presence  of  hydrogen  gas,  under  pressure,  the  oil  being 
heated  to  a  temperature  of  160  degrees  Centigrade,  would  produce  a  com- 
mercial lard  substitute?  A.  Yes. 
*  *  *  *  *  *  ** 

Q265.  Is  it  your  opinion  that  a  product  having  a  melting  point  of,  say, 
for  example,  42  degrees  Centigrade,  and  produced  by  treating  cotton- 
seed oil  with  hydrogen  in  the  presence  of  an  atmosphere  of  compressed 
hydrogen,  and  in  the  presence  of  nickel  deposited  upon  kieselguhr,  and 
maintained  in  suspension  in  the  oil  by  agitation,  the  oil  being  heated 
to  a  temperature  of  155  degrees  or  160  degrees  Centigrade,  and  without 
being  subjected  to  treatment  to  remove  the  characteristic  taste  and  odor 
due  to  hydrogenation,  would  be  commercially  acceptable  as  a  fat  for  use 
in  frying,  or  as  a  fat  for  use  in  shortening  dough? 

Mr.  Allen:  The  question  is  objected  to  as  incompetent,  indefinite  and 
misleading;  also  as  irrelevant  and  immaterial. 

A.  Why,  I  would  consider  such  a  product  entirely  edible;  but  to  be  a 
commercial  success,  it  would  be  preferable  to  subject  the  product  to  the 


674  APPENDIX 

treatment  to  which  lard  and  other   cooking  fats  are   regularly   subjected 
or  usually  subjected. 

Burchenal  states  that  the  process  practiced  by  Kayser  is  the  same  process 
described  in  Kayser 's  patent  1,008,474,  and  is  the  same  described  in  the  patent 
in  suit,  as  follows: 

Q754.  Referring  now  to  Questions  264  and  265,  is  the  process  described 
in  the  Kayser  patent  1,008,474  materially  different  from  the  process 
practiced  by  Mr.  Kayser  in  the  early  part  of  1908?  A.  As  I  under- 
stand the  patent,  it  is  not  materially  different. 

Q755.  That  is,  the  process  which  is  described  by  Mr.  Kayser  in  this 
patent  is  not  materially  different  from  the  process  which  he  practiced  in 
the  early  part  of  1908  at  the  Procter  &  Gamble  Company's  factory?  A. 
Yes. 

Q758.  Referring  now  to  Question  334,  is  there  any  difference  in  the 
process  of  hydrogenation  described  in  the  patent  in  suit  and  the  process 
which  was  carried  out  by  Mr.  Kayser  in  the  early  part  of  1908?  A.  As 
I  understand  that  paragraph,  it  does  not  refer  to  any  special  process, 
except  where  it  says  "preferably";  but  preference  was  given  to  the 
process  in  a  general  way  as  outlined  in  the  Kayser  patent. 

Q757.  That  is,  so  far  as  the  process  is  described  in  the  patent  in  suit, 
it  is  the  same  process  which  Mr.  Kayser  had  carried  on  in  the  early  part 
of  1908  in  the  hydrogenation  of  oils,  and  particularly  cotton-seed  oil? 
A.  The  process  of  hydrogenating,  yes. 

Q758.  And  your  knowledge  of  this  process  was  gained  from  Mr.  Kayser? 
A.  Yes. 


From  January  to  May,  1908,  Kayser  made  quite  a  large  amount  of  hydro- 
genized  refined  cotton  seed  oil  by  his  process  and  apparatus  and  in  May  of  that 
year  some  450  pounds  thereof  was  sent  by  Mr.  Procter  to  the  McCaw  Mfg.  Co., 
at  Macon,  Georgia,  to  have  it  made  up  into  lard  compound  by  substituting  it 
for  the  usual  oleo  stearine.  At  that  time  the  McCaw  concern,  of  which  W.  E. 
McCaw  was  president,  was,  and  for  a  long  period  thereto  had  been,  manufac- 
turing a  lard  substitute,  consisting  of  cotton  seed  oil  which  was  hardened  to  lard 
consistency  by  the  addition  of  a  hard  fat, — oleo  stearine.  This  material  was 
kriDwn  under  McCaw's  brand  of  "  Flake  White."  McCaw  at  that  time,  had 
nsver  met  Burchenal,  but  was  slightly  acquainted  with  Procter.  .D.  R.,  page 
302,  Q313.  It  seems,  according  to  McCaw's  story  that  in  February  or  March, 
1908,  Procter  called  at  McCaw's  New  York  office,  showed  him  a  sample  of  oil 
which  had  been  hydrogenized  by  Kayser,  and  in  effect  asked  him  if  he  would 
substitute  the  hydrogenized  oil  for  oleo-stearine  in  making  up  some  lard  sub- 
stitute. McCaw,  now  largely  interested  in  the  Procter  &  Gamble  Company, 
says  that,  at,  the  time  he  said  he  thought  the  material  would  be  unsuitable; 
but  naturally  his  recollection  on  this  point  would  tend  .to  be  influenced  by  his 
interests.  But  Procter  has  not  "  the  slightest  remembrance  "  of  what  he  said  to 
McCaw,  and  could  not  "  relate  the  circumstances  "of  the  meeting  with  McCaw. 
D.  R.,  page  213,  Qs.  30-35.  He  gave  no  hint  or  instructions  to  McCaw  as  to 
what  McCaw  should  do — how  to  mix  the  hydrogenized  fat  and  cotton  seed  oil 
or  the  proportions — but  left  the  whole  matter  to  McCaw.  Burchenal  had  no 


EDIBLE   HYDROGENATED   FATS  675 

hand  in  the  matter  whatever,  and  it  does  not  even  appear  that  he  claims  to  have 
asked  or  suggested  to  Procter  to  see  McCaw,  or  to  have  McCaw  make  any 
compound. 

Subsequently,  in  May,  1908,  as  previously  stated,  450  pounds  of  Kayser's 
hydrogenized  oil  was  sent  to  McCaw  who  substituted  it  for  oleo-stearine  in 
the  production  of  a  lard  substitute,  and  produced  3,000  pounds  of  such  lard 
substitute,  in  three  batches  of  1,000  pounds  each.  The  batches  varied  some- 
what in  the  proportions  of  the  hydrogenized  fat  to  the  liquid  cotton  seed  oil, 
one  batch  containing  10%  of  the  fat,  another  12%  and  a  third  14%. 

Q277.  You  were  left  to  your  own  resources  in  making  up  the  mixture? 
A.  Oh,  absolutely,  at  that  time.     McCaw,  D.  R.,  page  295. 

McCaw  testified  that  he  followed  the  usual  method  of  mixing  the  fat  with 
the  cotton  seed  oil  according  to  the  titer  of  the  former,  first  melting  the  fat, 
and,  after  blending  it  with  the  oil,  subjecting  the  mixture  to  the  usual  deodor- 
izing, refrigerating  and  aerating  treatments  to  which  Flake  White  had  long  been 
subjected.  McCaw  was  evidently  proud  of  his  reputation  as  a  lard  substitute 
manufacturer,  and  of  his  Flake  White,  and  did  not  care  to  put  out  a  lard  sub- 
stitute which  was,  according  to  his  notions,  not  as  good  as  Flake  White.  He  was, 
he  says,  not  satisfied  with  these  three  batches  made  in  May,  1908,  because  he 
regarded  them  as  "  unmerchantable,"  the  texture  was  "  grainy,  lumpy "  and  it 
was  "  entirely  too  dark."  On  being  questioned,  he  refused  to  state  how  the 
batches  were  deodorized,  as  this  process  was  and  is  "  a  secret  one  "  which  they 
still  guard  "  jealously."  He  says  the  material  then  made  was  sold  in  bulk  to 
some  soap-makers — whose  names  he  does  not  remember.  McCaw  said  he  cooked 
some  biscuits  with  the  compound  and  fried  potatoes,  but  that  they  were  unsatis- 
factory. Burchenal  at  one  time  said  that  the  McCaw  experiment  was  a  "  failure," 
and  that  the  material  appeared  "  stringy "  but  he  was  "not  a  judge  of  the 
material,  not  having  had  any  experience  (italics  ours).  Compare  these  statements 
of  McCaw  and  BurchenaPs,  however,  with  this  further  statement  of  Burchenal  in 
contradiction  (italics  ours). 

Q1025.  Referring  now  to  the  sample  of  the  mixture  that  Mr.  McCaw 
made,  using  the  hydrogenized  cotton-seed  oil  which  was  sent  him  in  the 
early  part  of  May,  1908,  which  sample  you  said  you  thought  you  saw, — 
was  that  sample  edible?  A.  I  presume  it  was. 

Q1026.  That  is,  you  regarded  it  as  an  edible  fat  product? 

Above  question  is  objected  to  as  incompetent  and  irrelevant. 

A.  I  do  not  recall  any  tests  being  made  on  it;  I  merely  presume  that 
it  was. 

Q1027.  So  far  as  the  edibility  of  it  was  concerned,  however,  you  were 
satisfied  that  it  was  edible? 

Above  question  is  objected  to  as  incompetent  and  irrelevant. 

A.  There  was  no  question  raised  in  my  mind  as  to  its  being  edible. 

Q1028.  I  show  you  a  certified  copy  of  the  Declaration  of  Interference 
dated  January  3,  1913,  in  the  matter  of  the  Interference  of  Ellis  vs. 
Boyce  vs.  Burchenal,  No.  35,642  in  which  your  application  Serial  No. 
591,721,  which  subsequently  eventuated  into  Letters  Patent  No.  1,135,935, 
was  involved,  and  in  which  it  appeared  that  the  issues  were  as  follows: 


676  APPENDIX 

Count  1 : 

An  edible  oil  product  comprising  hydrogenated  cotton-seed  oil  and 
edible  oily  material  blending  therewith. 

Count  2: 

An  edible  oil  product  of  lard-like  consistency  comprising  edible  hydro- 
genated oil  and  edible  oily  material  blending  therewith. 

I  also  show  you  a  certified  copy  of  the  preliminary  Statement  of  John 
J.  Burchenal,  dated  February  15,  1913,  filed  in  that  Interference,  in  which 
you  state  that  the  food  product  set  forth  in  the  Declaration  of  Inter- 
ference "  was  made  up  in  the  latter  part  of  May,  1908,  and  tested  at 
Macon,  Georgia."  Was  that  material  of  which  a  sample  was  sent  you 
by  Mr.  McCaw,  the  product  to  which  you  referred  in  that  Preliminary 
Statement?  A.  I  presume  it  was. 

Q1029.  Then  at  the  time  of  swearing  to  that  Preliminary  Statement, 
you  regarded  the  material  which  had  been  made  by  Mr.  McCaw  at 
Macon,  Georgia,  using  the  hydrogenated  oil  which  was  sent  him  in  the 
early  part  of  May,  1908,  as  an  edible  product  of  lard-like  consistency, 
comprising  edible  hydrogenated  oil  and  edible  oily  material  blending 
therewith,  did  you?  A.  I  think  so. 

Q1030.  Well  that  is  the  fact,  is  it  not?  A.  The  fact  was  that  I  thought 
so. 

Q1031.  Do  you  still  think  so?    A.  I  still  think  so. 

Note.  That  the  hydrogenized  cottonseed  oil  referred  to  was  produced  by 
Kayser,  with  Kayser's  process  and  by  Kayser's  machine,  on  Kayser's  own  initia- 
tive, and  was  edible,  and  that  Burchenal  makes  no  claim  of  having  caused  it  to 
be  sent  to  McCaw.  It  may  well  be  that  Mr.  Kayser  suggested  that  this  be  done. 

Kayser  continued  to  produce  his  hydrogenized  product,  and,  in  August,  1908, 
a  second  batch  of  1,000  pounds  thereof  was  sent  to  McCaw  at  Macon,  and 
10,000  pounds  of  compound  was  made,  by  mixing  the  hardened  fat  with  cotton 
seed  oil,  about  the  first  of  September.  McCaw  made  some  changes  in  the  speed 
of  the  refrigerating  rolls,  and  the  speed  of  the  picker  shaft  in  the  aerating  appa- 
ratus, and  while  the  compound  was  improved  in  appearance  over  that  made  in 
May  he  still  regarded  it  as  "  not  merchantable."  But  the  hydrogenized  fat  was 
substantially  the  same  as  that  which  had  previously  been  sent  him,  and  both 
were  edible,  for  Burchenal  testified  (italics  ours) : 

Q1060.  Now,  at  the  time  you  sent,  or  Mr.  Procter  or  the  Procter  & 
Gamble  Company  sent  that  first  batch  of  hardened  cottonseed  oil  to 
Mr.  McCaw,  had  you  made  up  your  mind  that  hydrogenized  oil  produced 
by  Kayser  was  an  edible  oil? 

A.  I  had. 


"  Q992.  *  *  *  A.  *  *  *Asa  matter  of  fact  at  the  time,  March 
5,  1908,  Mr.  Kayser's  real  interest  was  centered  in  the  production  of  a 
catalyst.  He  had  no  question  about  being  able  to  make  a  hard  fat  when  his 
catalyzer  was  right. 


EDIBLE   HYDROGENATED   FATS  677 

Q993.     And  he  knew  that   he   could  make  a  fat   of  any  consistency    he 
wanted,  if  his  catalyst  was  right? 
A.  /  suppose  so. 

*     *     * 

During  the  fall  and  winter  of  1908  and  1909,  Procter  &  Gamble  Co.  erected 
a  large  plant  for  the  hydrogenation  of  oils — reproducing  on  a  large  scale  the  small 
plant  which  Kayser  made  in  December,  1907,  and  January,  1908.  This  plant 
was  started  in  operation  February  15,  1909. 

Anderson  and  Kayser  were  at  work  on  the  large  plant  for  about  six  months, 
and,  as  Anderson  says,  it  was  "  the  equivalent  of  the  first  plant  on  an  enlarged 
scale,"  and  in  March,  1909,  a  carload  lot  of  the  Kayser  hardened  cottonseed  oil 
was  shipped  to  the  McCaw  plant  in  Macon.  This  hardened  cottonseed  oil 
shipped  in  March,  1909,  Burchenal  says  was  no  different  from  that  made  by 
Kayser  and  shipped  to  McCaw  in  May,  1908: 


In  the  meantime  Procter  &  Gamble  Company  had  purchassd  in  January,  1909, 
the  McCaw  Manufacturing  Company,  and  had  secured  the  services  of  McCaw. 
The  carload  of  hardened  fat  was  made  into  lard  compound  by  McCaw,  by  mixing 
it  with  cottonseed  oil  and  oleo  stearine,  substituting  the  hardened  fat  for  a  por- 
tion of  the  oleo  stearine.  This  compound,  McCaw  did  not  consider  as  good  as 
his  regular  Flake  White,  as  he  was  "  uneasy  about  the  quality "  but  it  was 
placed  on  the  market  and  sold  under  the  brand  "  Flake  White." 


The  oleo  stearin  was  entirely  left  out  of  Flake  White  in  1912,  but  no  one 
ever  knew  of  the  difference  between  the  original  Flake  White,  consisting  of 
cottonseed  oil  and  oleo  stearin,  that  consisting  of  cottonseed  oil,  oleo  stearin 
and  hydrogenized  fat,  and  that  finally  consisting  of  cottonseed  oil  and  hydro- 
genized  fat. 

*     *     * 

In  Burchenal's  long  examination,  he  was  given  over  and  over  again  an  invi- 
tation to  say  what  he  did,  what  he  contributed  to  Kayser's  product,  and  the 
most  that  he  could  say  was,  and  that  is  apparently  his  whole  case — that  he 
made  up  his  mind  that  it  was  edible.  Not  as  a  result  of  food  experiments,  or 
cooking  experiments,  but  only  that  he  thought  it  might  be  edible.  He  does  not 
say  he  sent  the  material  to  McCaw  or  suggested  its  being  sent.  It  was  Kayser's 
product,  and  it  was  Procter  who  saw  McCaw  and  sent  the  product  to  him. 


We  tried  to  get  Kayser  to  tell  his  story,  but  he  was  in  a  German  detention 
camp  in  England,  and  refused  to  talk  (Barrows'  testimony).  But  Kayser's 
friend,  Clarence  Von  Phul,  with  whom  Kayser  boarded  in  Cincinnati  from 
November,  1907  to  March,  1908,  testified  that  Kayser  knew  his  products  were 
edible,  as  follows  (italics  ours): 


Q13.  Did  you  know  where     Mr.  Kayser  was  employed  at  that  time? 
A.  Procter  &  Gamble  Company,  at  Cincinnati. 


678  APPENDIX 

Q14.  What  work  was  he  doing,  if  you  know? 

A.  He  was  getting  up  a  patent  for  a  food  product,  he  so  informed  me. 

*  *     * 

Q17.  Just  what  did  he  tell  you  about  this  matter? 

A.   He  said  that  he  was  producing  a  food  product  from  cotton-seed  oil  by 

a  chemical  action. 

*  *     * 

Von  Phul  was  sufficiently  in  Kayser's  confidence  that  Kayser  had  him  make 
the  sketches  or  drawings  which  were  used  by  the  patent  solicitor  in  preparing 
the  drawings  for  Kayser's  patent  No.  1,004,035,  which  was  applied  for  March  20, 
1908. 

Von  Phul  said  that  the  sample  Kayser  showed  him  "  looked  like  tallow " 
but  Kayser  said  it  was  a  food  product. 

*  *     * 

Kayser  had  no  confidants  except  Von  Phul,  no  one  else  knew  about  his  process 
and  his  products  except  Burchenal,  his  right-hand  man  Anderson,  and  Procter, 
who  seems  to  have  a  poor  memory.  The  whole  thing  was  kept  a  secret  by  the 
Procter  &  Gamble  Company,  who  "  would  have  arrested  any  one  seen  talking  with 
Kayser,"  and  the  secrecy  is  maintained  to  this  day.  But  enough  has  been  drawn 
out  of  those  men,  after  Judge  Hollister  issued  an  order  to  compel  them  to  answer, 
to  show  that  if  any  credit  is  due  to  any  one  at  Procter  &  Gamble  Company's 
factory,  for  the  production  of  food  products  by  the  hydrogenation  of  cotton-seed 
oil,  it  is  due  to  Kayser,  who  brought  the  process  and  products  from  Crosfields'  in 
England.  Procter  &  Gamble  had  to  square  the  matter  with  Crosfields'  later  on, 
but,  as  Kipling  says,  "  that  is  another  story." 

Kayser  returned  to  England  in  July,  1910,  and  when  he  was  out  of  the  coun- 
try Burchenal  filed  the  application  for  the  patent  in  suit. 

*  *     * 

In  any  event  this  defendant  has  proved  that  Burchenal  made  no  inventive 
act,  and  made  no  invention  or  discovery  whatsoever.  Burchenal  does  not  inti- 
mate that  he  suggested  any  after  treatment  for  the  hydrogenized  product,  or 
the  use  of  a  refined  oil,  or  even  its  use  in  the  manufacture  of  a  cooking  fat,  or 
that  he  made  any  tests  in  cooking  or  otherwise.  He  knew  nothing  about  the 
subject  except  what  Kayser  told  him. 


"  LARD-LIKE  "  FATS 

The  plaintiff  may  contend  that  Kayser's  semi-solid  product  is  not  "  lard-like." 
If  "  lard-like  "  has  any  special  significance  in  the  Burchenal  patent  it  infers  a 
product  which  is  low  in  linolin  and  high  in  olein,  and  with  not  over  25%  saturated 
fats. 

Burchenal,  in  his  testimony,  however,  thus  variously  defines  "  lard-like  "  (italics 
ours) : 

Q486.  How  did  you  know  whether  or  not  they  (partially  hydrogenized 
products)  were  lard-like,  without  testing? 
A.  From  appearance. 


EDIBLE  HYDROGENATED   FATS  679 

Q488.  What  is  the  physical  appearance  of  lard? 

A.  Well,  it  is  a  material  that  is,  according  to  my  views  of  lard,  in  a  general 
way,  it  is  something  that  is  soft  to  the  feeling,  at  a  normal  temperature, 
has  a  translucent  whitish  appearance,  it  is  not  hard  or  brittle  and  it  has 
a  certain  kind  of  plasticity  to  it.  It  is  not  granular,  but  lends  itself  to  mould- 
ing. I  suppose  you  might  say  it  is  homogeneous.  It  is  of  peculiar  quality, 
I  suppose;  it  is  the  one  that  of  all  the  natural  fats  has  made  it  adaptable  for 
domestic  purposes  in  cooking. 

Q489.  How  does  that  description  which  you  have  given  differ  from  the 
lard  compound? 

A.  Lard  compound  is  quite  different  in  appearance.  Lard  compound  is 
softer  than  lard  itself;  the  fats  have  not  the  same  characteristic;  lard  com- 
pound is  not  of  translucent  appearance;  it  has  a  foamier  look  to  it;  it  has 
not  the  same  consistency.  I  don't  think  anybody  that  is  familiar  with  both 
of  them  would  confuse  one  with  the  other. 

*     *     * 

BURCHENAL  MADE  No  CONTRIBUTION  TO  THE  ART 

He  was  not  versed  in  the  manufacture  of  lard  substitutes,  for,  as  he  says, 
"  I  was  not  altogether  familiar  with  the  manufacture  of  compound." 

He  knew  nothing  about  the  hydrogenation  of  oils  except  what  he  learned  from 
Kayser.  He  never  saw  hydrogenized  products  until  Kayser  showed  them  to  him. 
So  far  as  the  Record  shows,  he  has  never  himself  hydrogenized  any  oil  or  directed 
or  supervised  the  hydrogenation  by  others. 

He  was  not,  so  far  as  the  Record  shows,  a  scientist,  a  chemist,  or  even  one 
"skilled  in  the  art"  of  making  food  products.  Up  to  March,  1909,  the  Proc- 
ter &  Gamble  Company  made  soap,  not  food  products. 

Burchenal  admits  that 

(1)  He  does  not  know  the  "  saponification  value  "  of  cottonseed  oil. 

(2)  He   does   not   know  whether   hydrogenization   changes   the   saponification 
value  of  cottonseed  oil. 

(3)  He  does  not  know  the  temperatures  to  which  the  refrigerating  rolls  for 
the  product  must  be  chilled,  but  he  thinks  the  temperature  of   the  rolls   is  an 
important  feature  in  making  the  product  "  lard-like." 

(4)  He  does  not  know  what  effect  a  variation  in  the  pressure  during  hydro- 
genation may  have  upon  the  product. 

(5)  He  does  not  know  what  effect  a  variation  in  the  temperature  during  hydro- 
genation may  have  upon  the  resultant  product. 

(6)  He  does  not  know  what  effect  a  variation  in  the  proportion  of  catalyst  to 
oil,  during  the  hydrogenation,  may  have  upon  the  resultant  product. 

(7)  He  does  not  know  what  effect  a  variation  in  agitation  during  hydrogena- 
tion of  oil  may  have  on  the  resultant  product. 

(8)  He  does  not  know  the  proportions  of  hardened  or  hydrogenized  fat  to  oil, 
as  they  were  mixed  by  McCaw  in  1908;    he  didn't  see  the  mixing;    he  does  not 
know   what  was  done  with  the  material  made  by   McCaw;   he  does  not  know 


680  APPENDIX 

whether  the  hydrogenated  fat  sent  McCaw  was  deodorized  or  whether  McCaw 
deodorized  the  compound  made  therefrom;  and  he  does  not  know  what  tests 
McCaw  made. 

(9)  He  does  not  recall  (and  this  after  long  fencing  on  his  part)  whether  he 
knew  the  proportions  of  the  component  glycerides  of  the  product  described  in 
the  patent  in  suit,  before  he  filed  the  application  for  the  patent  in  suit. 

Q828.  Under  date  of  November  20,  1912,  the  composition  of  the  par- 
tially hydrogenized  oil  obtained  by  analysis  of  the  product  prepared  in 
the  manner  described  in  the  specification  of  the  patent  in  suit  was  stated 
to  be  as  set  forth  in  lines  10  to  18,  inclusive,  page  2,  of  your  Letters 
Patent  in  suit.  Did  you  make  the  analysis? 

A.  I  didn't. 

Q829.  Did  you  see  the  analysis  made? 

A.  No. 

Q830.  Or  check  them? 

A.  No. 

Q831.  Do  you  know  who  made  them? 

A.  No. 

(10)  He  does  not  know  who  made  the  "  re-determinations  of  the  melting  point 
and  titer  corresponding  to  the  iodine  value  of  55  and  80  in  partially  hydro- 
genized cottonseed  oil "  given  in  the  affidavit  of  Feb.  17th,  1915,  which  was  his 
affidavit  required  by  the  Examiner  before  allowing  the  patent  in  suit  but  sup- 
poses "  that  things  were  based  on  our  determinations  at  Ivorydale,"  but  he  did 
not  make  them  and  does  not  know  who  did. 

(11)  Burchenal   further   admits   on   examination   that   he   does   not   know   at 
what  melting  point  the  product  of  his  patent  hi  suit  would  cease  to  be  "  lard- 
like,"  or  whether  the  product  having  an  iodine  value  of  55  would  be  a  semi- 
solid  at  ordinary  temperatures. 

(12)  Again  he  does  not  know  what  is  necessary  to  produce  his  alleged   prod- 
uct.    (Italics  ours.) 

Q856.  In  the  production  of  a  partially  hydrogenized  cottonseed  oil 
what  factors  are  necessary  to  insure  in  the  product  a  high  olein  content 
and  a  low  linolin  content? 

A.  I  can't  tell  you. 

Q857.  You  mean  that  you  don't  know? 

A.  /  don't  know. 

Q858.  And  never  did  know? 

A.   Never  did  know. 

(13)  Burchenal  admits  that  he  does  not  recall  giving  instructions  to  McCaw 
as  to  the  products  McCaw  made  in  1908.     He  does  not  recall  making  or  super- 
vising any  cooking  tests  with  hydrogenized  oils,  until  after  Flake  White,  containing 
hydrogenized  oil  was  put  on  the  market  following  February  15,  1909. 

NOTE. — The  hydrogenized  fat  was  placed  on  the  market  before  any  cooking 
tests  with  them  were  made  by  Burchenal,  who  was  ignorant  of  McCaw's  tests. 
And  there  was  no  material  difference  between  that  hydrogenized  fat  and  the  fats 
which  had  been  brought  to  this  country  by  Kayser,  and  which  were  made  here, 
in  January,  1908,  by  Kayser. 


EDIBLE   HYDROGENATED   FATS  681 

(14)  Burchenal  likewise  admits  that  he  does  not  know  whether  animal  oleo- 
stearin  is  edible — he  presumes  it  is  but  is  not  certain. 

(15)  He  says  he  does  not  think  any  animal  or  vegetable  fatty  acid  or  gly- 
eerides  of  any  animal  or  vegetable  fatty  acids  when  hydrogenized,  are  suitable 
for  use  as  food  products,  Q1005,   D.  R.,  p.  248,  and  denies  that  a  food  com- 
pound closely  simulating  lard  can  be  made  by  a  mixture  of  any  oil  and  a  harden- 
ing agent  produced  by  hydrogenating  any  oil  or  liquid  fat. 

(16)  He  does  not  know  whether  the  iodine  value  of  a  product  is  one  of  its 
physical  constants. 

(17)  And  he  never  effected  the  separation  of  the  liquid  fatty  acids  of  any 
cottonseed  oil  treated  by  hydrogen. 

(18)  He   was   asked    when   he   first    produced    a    homogeneous   lard-like   food 
product  consisting  of  an  incompletely  hydrogenize^  oil. 

Why  I  had  done  a  good  deal  of  experimental  work  on  the  material; 
I  think  I  am  safe  in  saying  that  the  date  on  which  that  material  was  first 
produced  hi  any  appreciable  quantities  was  after  April  26,  1910,  and  in  all 
probability,  prior  to  July  1,  1910. 

*  *     * 

(But  Kayser  had  already  disclosed  to  Burchenal  semi-solid  products  of  hydro- 
genated  cotton  seed  oil — those  he  brought  from  England,  and  those  made  by 
him  March  5,  1908,  which  had  melting  points  of  42°  C.  and  43°  C.) 

(20)  Burchenal  was  asked  what  experiments  he  made  with  a  mixture  of  the 
hard  Kayser  product  and  cotton  seed  oil,  if  any,  and  this  is  how  he  testified: 

Q895.  Now,  when  the  first  experiments  were  made  with  hardened 
cottonseed  oil,  by  compounding  it  with  other  cottonseed  oil,  what  did  you 
do  to  the  product,  other  than  mixing  the  ingredients  together?  A.  / 
don't  recall  that  we  did  anything  beyond  the  mixing  of  the  oil. 

*  *     * 

The  fact  is  that  really  Burchenal  had  nothing  to  do  with  any  experimentation 
involving  hydrogenization  that  was  going  on,  in  spite  of  vague  references  to 
the  "  experiments  "  "  we  "  made. 

Morrison  let  the  real  truth  slip  out.     He  was  asked: 

Q169.  Who  was  actually  doing  the  experimentation  in  hydrogenizing  oils 
in  the  laboratory? 

A.  At  what  period? 

Q170.  Prior  to  Nov.  10,  1910? 

A.  Mr.  Kayser  up  to  the  time  he  left  in  1910,  and  after  that  Mr.  Graff 
with  the  assistance  of  boys  who  were  employed  in  the  laboratory. 

Kayser  left  this  country  in  July,  1910. 

(21)  Burchenal  introduced  the  new  matter  regarding  the  proportions  of  com- 
ponent  glycerides   in   his   application   for   patent   on    November   20,    1912.     He 
admitted  that  he  had  not  ascertained  these  proportions  by  his  own  work  but 
through  the  work  of  others,  but  he  didn't  know  how  they  were  ascertained,  or 
who  found  them  out,  or  when  he  got  the  information. 

Morrison  says  he  doesn't  know  who  made  the  determinations,  Qs86-88,  D.  R., 
pp.  326,  327,  from  which  the  percentages  of  component  glycerides  were  figured, 


682  APPENDIX 

but  that  he  himself  made  the  figures,  that  they  were  made  from  some  memo- 
randa which  he  has  lost,  and  he  would  or  could  not  say  positively  that  the  pro- 
portions or  percentages  were  worked  out  prior  to  the  filing  of  the  application 
for  the  patent  in  suit. 

Bid  it  was  Kayser  who  was  "  doing  the  experimentation  in  hydrogenizing  oils 
in  the  laboratory." 

If  anything  is  clear,  it  is  that  while  Burchenal  talks  vaguely  of  "  experi- 
ments," which  "we"  made,  he  really  never  did  anything  that  can  be  placed 
to  his  credit,  or  which  shows  any  inventive  act  or  deed  on  his  part.  His  gen- 
eral ignorance  on  the  subject  is  manifest.  His  admissions  demonstrate  lack  of 
originality.  One  will  search  the  record  in  vain  to  find  any  evidence  entitling 
him  to  be  ranked  as  an  inventor.  It  is  only  to  inventors  that  valid  letters  patent 
can  be  granted  under  the  statutes.  Kayser,  so  far  as  Burchenal  was  concerned, 
was  the  source  of  all  of  his  information.  Kayser  disclosed  to  him  the  process, 
the  apparatus,  the  edible  product,  and  Kayser  carried  on  exclusively  the  ex- 
perimentation in  hydrogenation  without  any  suggestion  from  Burchenal.  Sup- 
pose there  were  a  direct  contest  between  Kayser  and  Burchenal  as  to  the  inven- 
torship  of  the  white  or  yellowish  semi-solid  produced  by  the  partial  hydrogena- 
tion of  cottonseed  oil — could  there  be  any  doubt  as  to  the  outcome?  The  very 
first  product  which  Kayser  showed  Burchenal  was  such  a  product  and  Burchenal 
admits  it  was  edible.  Would  any  Court  give  priority  of  invention  to  Burchenal? 
If  priority  could  not  be  awarded  Burchenal  in  that  case  he  certainly  cannot  be 
held  to  be  the  inventor  of  that  same  product  in  the  case  at  bar. 

The  record  clearly  shows  that  Burchenal  has  no  standing  as  an  inventor  and 
consequently  the  patent  issued  to  him  is  void. 

*     *     * 

In  a  discussion  of  the  file  wrapper  and  contents  of  the  patent  in  suit,  the 
following  statements  appear  in  defendant's  brief: 

What  instantly  strikes  one  familiar  with  the  Kayser  patents,  and  the  processes 
therein  described,  and  the  solid  and  semi-solid  hydrogenized  cottonseed  oils 
produced  by  Kayser,  is  that  the  Burchenal  specification  as  filed  described  only 
what  Kayser  had  disclosed  to  him.  The  sample  of  hydrogenized  oil  which 
Kayser  brought  from  Crosfield  &  Sons  had  a  melting  point  of  39.3°  C.  and  an 
iodin  value  of  52.26,  a  little  less  than  55  which  Burchenal  mentioned  as  the  lower 
limit  in  his  original  specification.  One  is  also  struck  with  the  fact  that  the  preferred 
melting  point  of  the  semi-solid  product  originally  described  by  Burchenal,  is  the 
melting  point  of  one  of  the  two  products  produced  by  Kayser  on  March  5,  1908, 
the  other  Kayser  product  having  a  melting  point  of  43°  C.  which  was  the  upper 
limit  of  the  melting  point  range  originally  given  by  Burchenal. 

On  November  26,  1910,  before  the  case  was  acted  on  by  the  examiner,  the 
following  claim  was  added  to  those  on  file. 

3.  A  semi-solid  hydrogenized  oil. 

On  the  13th  of  December,  1910,  the  claims  were  rejected  by  Examiner  Ely 
on  U.  S.  patent  to  Schwoerer  No.  902,177,  the  Herf order  (Normann)  German 
patent  No.  141,029  and  the  Erdmann  German  patent  No.  211,669.  In  explana- 
tion Examiner  Ely  said  in  part: 

The  composition  of  lard  and  of  cotton  seed  oil  as  to  the  glycerine  olein 
and  stearin    that  they  contain   is  well  known.     To  make  a  product  from 


EDIBLE   HYDROGENATED    FATS  683 

cottonseed  oil   that   shall  simulate  lard,  the  content  of  stearin  should   be 
increased 

After  citing  the  patents  referred  to,  Examiner  Ely  further  said: 

It  is  thought  therefore  that  if  the  problem  of  simulating  lard  from 
cottonseed  oil  were  presented  to  an  oil  chemist,  an  incomplete  hydro- 
genation  of  the  cotton  seed  oil  would  at  once  suggest  itself  to  him  as  a 
solution  of  the  problem.  All  the  claims  are  accordingly  rejected  on  the 
above  ground  of  lack  of  invention." 

Burchenal  waited  until  the  last  moment  of  the  statutory  period  of  one  year 
allowed  for  the  filing  of  an  amendment  to  save  the  case  from  abandonment, 
and  on  December  13,  1911,  filed  an  amendment  cancelling  claim  3. 

By  the  cancellation  of  this  claim  he  admitted  that  semi-solid  hydrogenized 
products  were  old  in  the  prior  art.  The  prior  patents  to  Normann  and  Erdmann 
had  disclosed  semi-solid  products  produced  by  the  partial  hydrogenation  of  both 
animal  and  vegetable  oils. 

The  argument  filed  as  a  part  of  the  amendment  said  in  part: 

Applicant  does  not  allege  that  his  product  is  identical  with  lard,  for  it 
may  be  and  probably  is  impossible  to  artificially  reproduce  lard.  .  .  . 
Applicant  appears  to  be  the  first  to  determine  and  set  forth  the  advan- 
tages and  properties  of  a  fractionally-hydrogenized  product,  and  his  claims 
do  not  even  cover  such  product  broadly  but  are  limited  to  a  product  having  a 
definite  degree  of  partial  hydrogenation,  giving  it  definite  physical  and  chemical 
characteristics  specified  in  the  claims.  (Italics  ours.) 

(At  this  time  Burchenal's  claim  1  specified  a  range  of  36°-43°  C.  in  melting 
point,  and  claim  2  recited  specifically  a  melting  point  of  40°  to  21°  C.,  in  addi- 
tion to  the  iodin  value  range  of  55-80,  etc.  So  Burchenal  had  conceded  that  a 
food  product  consisting  of  partially  hydrogenized  oil  having  melting  points 
above  or  below  the  melting  point  range  given  by  him  and  having  iodin  values 
below  or  above  those  recited  by  him,  were  not  of  his  invention.) 

On  December  29,  1911,  the  Examiner  a  second  time  rejected  the  claims,  citing 
the  Kayser  patents  1,004,035  and  1,008,474,  and  pointing  out  that  Kayser 
described  hydrogenizing  cottonseed  oil,  and  that  Kayser's  process  could  be 
arrested  at  any  time  during  its  progress  to  produce  an  incompletely  hydrogenized 
article.  He  pointed  out  the  fact  that 

the  physical  constants  given  as  to  the  product  in  claim  2  are  not  seen  to  define 
anything  critical  or  decisive.     (Italics  ours.) 

and  rejected  the  claims  as  defining  nothing  patentable  over  the  disclosures  in 
the  Kayser  patents. 

(The  Examiner  was  thus  directing  special  attention  to  the  following  statements 
in  the  two  Kayser  patents.)  (Italics  ours.): 

The  time  of  treatment  will  vary  with  the  progress  realized  and  with 
the  degree  of  saturation  aimed  at.  Patent  1,004,035. 

*     *     * 

Again  Burchenal  let  the  matter  lie  dormant  for  ten  months  and,  on  November 
20,  1912,  more  than  two  years  after  he  filed  his  application,  filed  an  amendment 
in  which  he  presented  the  new  matter  containing  the  specific  reference  to  the 


684  APPENDIX 

particular  percentages  of  the  component  glycerids  supposed  to  identify  his 
product.  Defendant's  Exhibit  Book,  page  14.  In  the  meantime  Carleton  Ellis 
had  been  granted  a  patent,  No.  1,038,545,  for  a  butter  substitute  by  an  Exam- 
iner in  another  division  (No.  6)  of  the  Patent  Office  separate  from  that  in  which 
Burchenal's  application  was  pending.  In  this  patent,  Ellis  pointed  out  the 
desirability  of  having  his  butter  substitute  melt  at  a  temperature  below  the 
heat  of  the  human  body. 

In  the  amendment,  dated  November  20,  1912,  Exhibit  Book,  page  14,  Bur- 
chenal  presented  present  claims  5  to  7,  inclusive,  directed  to  the  specific  com- 
position of  his  product,  changed  the  numerals  of  his  original  claims  1  and  2  to 
3  and  4,  respectively,  and  presented  two  new  claims  copied  from  this  Ellis 
patent.  Not  for  a  lard  substitute,  but  for  a  butter  substitute,  as  follows: 

1.  A  butter-like  composition  comprising  edible  hydrogenized  fatty  oil. 

2.  A   butter-like   composition   comprising   edible    hydrogenized   vegetable 
oil. 

In  order  to  lay  a  basis  for  these  claims  in  the  new  matter  presented  by 
amendment,  there  was  included  the  phrase,  "  but  below  the  heat  of  the  blood " 
after  the  word  "  temperatures  "  in  line  74,  page  1,  and  line  26,  page  2,  of  the 
printed  copy  of  the  patent. 

By  this  same  amendment  he  changed  the  preferred  melting  point  of  41°-42°  C. 
in  his  original  claim  2  to  36°-43°  C. 

Burchenal's  application  was  transferred  to  Division  6  to  Examiner  Lewers, 
who  had  permitted  the  Ellis  patent  to  issue,  and  on  December  6,  1912, 
Examiner  Lewers  wrote  Burchenal  that  there  was  no  basis  in  his  appli- 
cation for  the  new  claims  1  and  2  for  a  butter  substitute.  He  pointed  out 
that  a  butter  substitute  must  have  "  a  melting  point  considerably  less  than 
the  temperature  of  the  human  body  "  so  that  it  will  melt  in  the  mouth,  whereas 
the  minimum  melting  point  stated  originally  by  Burchenal  was  36°  C.  (or  97°  F.) 
was  not  "  considerably  below "  body  temperature,  and  the  preferred  melting 
point  41°-42°  (105.8°-107.6°  F.)  "are  much  above  the  normal  human  body  tem- 
perature." The  Examiner  accordingly  rejected  the  new  claims  1  and  2  both  as 
"  covering  new  matter  "  and  because  the  product  originally  described  by  Burch- 
enal was  not  butter-like. 

Touching  the  new  claims  5,  6  and  7  in  which  the  proportions  of  component 
glycerids  were  recited,  and  the  amendment  to  the  specification  setting  them  forth, 
the  Examiner  said: 

The  composition  was  not  originally  givea  and  the  Examiner  has  no 
means  of  determining  that  the  compound  having  the  properties  set  forth  in 
the  last  paragraph  of  page,  1,  and  the  first  paragraph  of  page  2  (to  wit,  one 
having  a  melting  point  ranging  from  36°  C.  to  43°  C.  preferably  41°-42° 
C."  ...  a  saponification  value  of  about  195,  an  iodin  value  ranging  from 
about  55  to  80,  and  a  titer  of  from  about  35.5°  C.  to  42.5°  C.")  would 
necessarily  have  the  composition  set  forth  in  the  amendment.  The  only 
ground  upon  which  the  statement  of  the  composition  can  now  be  inserted 
is  that  the  compound  having  the  properties  as  set  forth  in  the  case  as  filed 
must  have  the  composition  alleged,  and  proof  of  this  in  the  form  of  a  proper 
affidavit  must  be  filed.  (Italics  ours.) 


EDIBLE   HYDROGENATED    FATS  685 

The  Examiner  again  rejected  original  claims  1  and  2  on  the  Kayser  patent, 
calling  attention  to  line  15,  page  1,  and  lines  95  to  102,  page  2,  of  said  patent. 
These  lines  have  been  quoted  on  pages  142-143  of  this  brief. 

On  January  10,  1913,  Exhibit  Book,  page  21,  Burchenal  amended  his  new 
claims  1  and  2  by  changing  butter-like  to  "  lard-like,"  and  inserting  the  word 
lard-like  in  claims  3  and  4  (original  claims  1  and  2).  He  accepted  the  Kayser 
patents  as  prior  art.  How  could  he  help  it,  as  we  now  know  what  Kayser  had 
disclosed  to  him,  and  Burchenal  has  now  admitted  and  conceded  on  the  wit- 
ness stand. 

He  said  in  the  "  Remarks  "  accompanying  the  amendment: 

The  product  originally  described,  having  the  melting  point  tiler  and 
iodine  value  specified  in  original  claim  2  has  the  chemical  composition  set 
forth  in  claims  5,  6,  7. 

He  urged  that  the  product  of  claims  3  and  4  (original  1  and  2)  was  not  antici- 
pated because  Kayser  had  not  specifically  described: 

a  lard-like  food  product,  a  semi-solid  having  a  melting  point  ranging  from 
36°  C.  to  43°  C. 

Of  course,  the  Examiner  did  not  know  that  Kayser  had  produced  products 
of  melting  points  of  42°,  43°  C.  and  did  not  know  anything  about  Kayser's 
samples  brought  from  Crosfields;  so  on  February  15,  1913,  he  wrote  a  letter 
stating  that  when  the  supplemental  oath  was  filed  the  case  would  be  allowed. 

March  17,  1913.  Note  Burchenal's  next  move.  In  claim  3,  original  claim  1, 
he  cancelled  the  reference  to  the  melting  point  range  of  36°-43°  C.  and  substi- 
tuted a  reference  to  the  "  iodin  value  ranging  from  55  to  80."  He  said  in  his 
"  remarks:" 

these  products  have  no  sharp  or  definite  melting  point,  and  in  view  of 
the  variety  of  melting  point  methods  employed  by  chemists  and  the  dif- 
ferent values  obtained  thereby  claim  3  has  been  amended  to  specify  the 
range  of  iodin  values  of  applicant's  products  rather  than  their  melting- 
point  range. 

Thus  he  changed  the  specification  in  a  way  the  examiner  had  refused  to  per- 
mit him  to  do — to  insert  a  melting  point  temperature  "  considerably  lower " 
than  body  temperature.  He  filed  also  an  affidavit  that  the  subject  matter  pre- 
sented in  his  amendment  filed  November  20,  1912,  had  been  invented  before  he 
filed  his  application,  but  this  affidavit  was  in  support  also  of  the  claims  for  a 
"  butter-like  product. 

On  May  27,  1913,  the  examiner  suspended  further  action  on  the  merits,  since 
the  companion  application  (which  eventually  resulted  in  patent  1,135,935)  was 
involved  in  an  interference  with  an  issue  (see  claims  3  and  4  of  said  patent) 
over  which  the  then  claims  1  and  2  of  the  application  of  the  patent  in  suit 
were  "  not  patentable." 

The  case  was  then  suspended  until  January  22,  1915,  and  on  that  date  the 
examiner  called  attention  to  the  fact  that  Burchenal  had  not  yet  filed  the  affi- 
davit which  the  examiner  had  required  on  December  6,  1912,  that  the  product 
as  originally  filed  must  have  the  chemical  composition  recited  in  claims  5,  6  and 
7.  He  required  the  reference  to  the  product  as  "  congealing  below  the  heat  of 
the  blood  "  to  be  stricken  from  the  specification  as  amended. 


686  APPENDIX 

There  was,  at  this  time,  still  in  the  specification,  the  original  statement  of  the 
melting  point  range  of  36°-43°,  preferably  41°-42°  C.;  so  Burchenal  amended 
his  case  on  March  5,  1915,  by  cutting  out  of  the  original  specification  the 

reference  thereto. 

*     *     * 

Burchenal  also  cancelled  from  the  specification  the  reference  to  his  product 
congealing  below  blood  temperature. 

Up  to  this  time;  there  had  remained  in  the  original  specification  a  paragraph 
to  the  effect  that  the  product  could  be  produced  by  mixing  "unhydrogenized  oil 
and  a  hard  hydrogenized  product  having  a  melting  point  of  50°  C."  On  this  date, 
March  5,  1915,  Burchenal  cancelled  this  paragraph,  cancelled  his  claims  1  to  4 
(including  the  original  claims  and  the  first  and  second  claims  presented  November 
20,  1912),  and  presented  the  present  claims  1  to  4  as  they  now  appear  in  the 
patent. 

Now,  when  the  case  was  originally  filed  the  only  directions  given  to  produce 
the  "  white  or  yellowish  semi-solid  "  were  to  stop  the  reaction  when  the  product 
on  cooling  had  a  melting  point  of  36°  to  43°  C.— preferably  41°-42°  C.,  and 
these  products  were  said  to  have  an  iodine  range  of  55  to  80.  Burchenal  had 
not  said  to  "  stop  the  reaction  when  the  product  has  an  iodine  value  of  55  to  80," 
but  that  a  product  having  those  melting  points  would  have  that  range  of  iodine 
values,  and  he  had  persuaded  the  examiner  to  allow  his  claims  because  Kayser's 
patent  had  not  specifically  recited  these  melting  points  in  referring  to  his  "  semi- 
solid." 

Yet  Burchenal  in  his  amendment  lowered  the  titer  .5°  C.  and  changed  his 
specification  in  respect  of  the  melting  points,  and  reduced  the  whole  range  of 
36°-43°  C.  to  33°-40°  C.;  that  is,  he  had  lowered  it  3°  C.  (5.4°  F.)  so  as  to 
bring  the  range  down  to  as  low  as  33°  C.  (or  91.4°  F.  instead  of  97°  F.),  which 
is  very  much  below  blood  heat,  and  thus  he  did  the  very  thing  which  the  exam- 
iner had  said  he  would  not  be  permitted  to  do. 

He  said  in  his  "  remarks  "  (italics  ours) : 

Applicant's  affidavit  filed  herewith,  conforms  to  the  requirements  of 
the  examiner.  It  also  embodies  a  more  accurate  redelermination  of  the 
melting  point  and  titer  or  products  prepared  from  cottonseed  oil  and  having 
the  described  range  of  iodine  value.  While  the  new  figures  do  not  differ 
substantially  from  those  originally  given,  it  is  thought  desirable  to  substitute 

them. 

#     *     * 

The  history  of  the  prosecution  of  the  Burchenal  application  as  shown  by  the 
file  wrapper  and  contents  of  the  patent  in  suit  is  .a  strange  one.  The  case  had 
been  transferred  from  the  division  of  the  Patent  Office  headed  by  Dr.  Ely  to 
Division  6  headed  by  Mr.  Lewers.  Most  vital  changes  were  made  in  the  speci- 
fication and  claims — and  finally  without  a  supporting  or  supplemental  oath, 
the  patent  containing  these  changes  and  the  new  claims  in  suit,  was  permitted 
to  issue. 

These  claims  were  drawn  after  the  defendant's  product  was  on  the  market. 

From  a  consideration  of  the  file  wrapper  and  contents,  one  thing  is  certain; 
— Burchenal  insisted  that  his  product  had  and  must  have  20-25%  stearin, 
65-75%  olein  and  5-10%  linolm. 


i:    I1VDHOGENATED    FATS  687 

Another  thing  is  certain.  Burchenal  changed  the  description  of  his  process 
which  originally  told  one  attempting  to  produce  the  product  to  stop  the  reac- 
tion when  the  semi-solid  product  on  cooling,  had  a  melting  point  of  36°-43°  C., 
preferably  41°-42°  C.,  so  that  as  amended  and  issued  the  patent  contains  a 
wholly  inconclusive  and  ambiguous  statement  to  the  effect  that  the  operation  is 
stopped  when  the  oil  has  been  converted  into  a  product  which  cools  to  a  white 
or  yellowish  "  semi-solid  more  closely  resembling  lard  than  do  the  commercial  mix- 
tures of  cottonseed  oil  and  animal  oleo  stearin  ..."  (lines  89-94,  page  1  of  the 
printed  patent). 

He  thereby  renders  his  patent  vague  and  uncertain  in  its  description  how  to 
make  or  compound  the  product  and  leaves  one  to  experiment. 

Still  another  thing  is  certain.  Burchenal  lowered  the  melting  point  range  of 
his  alleged  new  product  5.4°  F.  and  the  titer  range  .5°  C.  and  thus  departed 
from  his  original  disclosure,  without  a  supplemental  oath. 

Patents  in  which  new  matter  is  thus  inserted  without  a  supplemental  oath, 
have  uniformly  been  held  to  be  invalid. 


We  confidently  assert  that  the  proceedings  in  the  Patent  Office  prior  to  the 
issuance  of  the  patent  in  suit,  were  such 

(1)  That  having  insisted  that  his  alleged  new  product  has  a  definite  chemical 
composition,  and  no  other,  he  cannot  be  heard  to  deny  it; 

(2)  That  nothing  can  be  held  to  infringe  his  claims  which  does  not  have  that 
definite  chemical  composition;    and 

(3)  That  Burchenal  made  radical  changes  in  his  specification  and  claims  as 
originally  filed,  which  were  unsupported  by  his  original  disclosure,  and  that  as  a 
result  his  patent  is  void. 

COMPARISON  OF  THE  PATENTED  PRODUCT  WITH  COMMERCIAL  LARD  SUBSTITUTES 

Considering  the  Burchenal  patent  from  the  point  of  view  advanced  by  Dr. 
Baskerville  that  the  purpose  of  the  patentee  is  to  increase  the  proportion  of  solid 
fat,  in  order  to  secure  the  semi-solid  consistency,  it  is  shown  by  the  record  that 
there  is  no  material  difference  between  the  product  therein  set  forth  as  so  con- 
sidered, and  those  lard  substitutes  which  for  many  years  have  been  commer- 
cially on  the  market.  In  fact  this  is  conceded  by  plaintiff's  experts,  Dr.  Basker- 
ville and  Mr.  Morrison. 

The  first  paragraph  of  the  specification  reads  as  follows: 

This  invention  is  a  food  product  consisting  of  a  vegetable  oil,  prefer- 
ably cottonseed  oil,  partially  hydrogenized  and  hardened  to  a  homogeneous 
white  or  yellowish  semi-solid  closely  simulating  lard. 

If  the  words  italicized — "  partially  hydrogenized  "  be  omitted,  that  descrip- 
tion fits  what  are  known  as  "  lard  compounds  "  or  "  lard  substitutes,"  such  as 
"  Jewel  compound,"  which  has  been  made  commercially  by  Swift  &  Company 
since  1890,  and  of  which,  according  to  Mr.  Richardson's  testimony,  Swift  & 
Company  produces  between  two  hundred  and  fifty  million  and  five  hundred 
million  pounds  annually.  T.  R.,  page  553,  Q15.  Such  lard  substitutes  consist 
of  cottonseed  oil  hardened  to  a  white  or  yellowish  semi-solid  simulating  lard,  by 


688  APPENDIX 

the  addition  of  10  to  15%  of  oleo  stearin,  which  is  a  hard  white  substance  pro- 
duced by  expressing  the  oil  from  beef  tallow.  This  substance  furnishes  the  addi- 
tional stearin  necessary  to  harden  the  cottonseed  oil  to  the  desired  stiffness  or 
semi-solidity. 

Mr.  McCaw  testified  that  for  many  years  prior  to  1908,  the  McCaw  Manu- 
facturing Company  manufactured  a  lard  compound  known  as  Flake  White, 
which  consisted  of  cottonseed  oil  hardened  or  stiffened  to  lard  consistency  by 
the  addition  of  high-grade  oleo  stearin  having  a  titer  of  53°  C.,  in  the  propor- 
tion of  20%  of  oleo  stearin  and  80%  refined  bleached  cottonseed  oil.  D.  R., 
p.  132,  Q21,  Q26.  The  proportions  of  cottonseed  oil  and  oleo  stearin  were  varied 
according  to  the  season  of  the  year,  more  of  the  stiffening  agent  being  added 

in  the  summer  than  in  the  winter. 

*  *     * 

The  record  further  shows  that  the  substitution  of  cottonseed  oil,  hydrogenized 
to  a  melting  point  of  55°  to  60°  C.,  for  oleo  stearin,  in  the  manufacture  of  Flake 
White,  made  no  material  change  in  the  resultant  product,  and  customers  never 

knew  the  difference. 

*  *     * 

It  is  clear  then  from  the  foregoing  that,  as  a  lard  substitute,  and  for  all  pur- 
poses to  which  such  materials  are  employed,  there  is  no  practical  difference 
between  a  compound  containing  oleo  stearin  and  one  containing  hydrogenized  oil 
of  the  same  or  similar  degree  of  hardness  or  solidity. 

Now,  it  is  customary  in  the  manufacture  of  lard  substitutes,  whether  oleo 
stearin  or  hydrogenized  fat  be  added  to  the  oil  to  stiffen  it,  to  vary  the  pro- 
portion of  the  stiffening  agent  according  to  its  titer  or  melting  point. 


It  appeared  from  the  testimony  at  the  trial  that  it  makes  no  difference,  so 
far  as  practical  results  are  concerned,  whether  the  cottonseed  oil  is  stiffened 
or  hardened  by  solid  fats  produced  by  partial  hydrogenation,  or  by  the  addition 
of  oleo  stearin,  or  by  the  addition  of  hydrogenized  fat.  Both  Dr.  Baskerville 
and  Mr.  Morrison  agree  on  this. 


Patent  not  Granted  on  Theory  of  Added  or  Increased  Stearin. 

In  the  foregoing  analysis  of  the  patent  in  suit  we  have  assumed  the  theory, 
advanced  by  Dr.  Baskerville,  that  the  only  purpose  set  out  in  the  patent  as  the 
result  of  partial  hydrogenation  is  the  addition  of  or  increase  in  the  proportion 
of  the  solid  fats  or  saturated  glycerides.  That,  however,  is  not  the  theory  on 
which  the  patent  was  granted,  and  in  fact  is  contrary  to  the  plain  and  unmis- 
takable terms  of  the  specification  itself.  Dr.  Baskerville  tried  to  give  the  im- 
pression that  the  patent  points  out  the  addition  of  the  glyceride  of  stearic  acid 
rather  than  palmitic  as  the  vital  feature  in  the  patented  product.  But  there  is 
not  a  single  word  in  the  specification  stating  that  solid  fats  or  stearin  are  added 

or  are  increased. 

*     *     * 

The  whole  stress  in  the  patent,  as  shown,  is  placed  on  reducing  the  linolin  to 
5  to  10%  and  increasing  the  olein  to  65  to  75%.  Not  a  word  is  said  directly 
about  "  increasing  "  the  solid  or  saturated  fats. 


EDIBLE   HYDROGENATED    FATS  689 

Moved  by  the  exigencies  of  the  case,  and  confronted  by  the  triangular  charts 
produced  by  Dr.  Walker  and  Mr.  Richter  which  were  predicated  directly  on 
the  three  components  specified  in  the  patent  in  suit,  and  which  prove  the  chem- 
ical dissimilarity  of  Kream  Krisp  and  the  product  of  the  patent  in  suit — Dr. 
Baskerville  hastily  built  up  a  theory  of  "  added  stearin."  Unfortunately  for  him 
he  based  his  whole  conclusions  upon  a  fundamentally  wrong  analysis  of  cottonseed 
oil  given  in  lines  18  to  23,  page  2,  of  the  patent  in  which  the  percentage  of 
saturated  glycerides  is  given  as  17%.  So  far  as  is  known  there  never  was  such 
a  cottonseed  oil  having  the  percentages  of  component  glycerides  given  in  the 
patent.  Dr.  Baskerville  had  never  seen  one,  he  admitted,  nor  had  Morrison  or 
any  one  else.  Dr.  Baskerville  evidently  had  not  read  Morrison's  deposition  taken 
.at  Cincinnati  in  which  he  explained  that  that  analysis  was  a  blunder. 

*  *     * 

Morrison  also  testified  that  the  cottonseed  oil  being  used  at  the  time  he  made 
that  analysis  had  iodine  values  of  108  to  110,  and  that  the  iodine  values  of  the 
liquid  fatty  acids  ranged  from  147  to  148.  He  gave  an  analysis  of  the  oil  like 
that  being  used,  as  48%  linolin,  29.6%  olein  and  21.8%  saturated  fats. 

It  is  of  record,  as  admitted  by  Dr.  Baskerville,  that  ordinary  cottonseed  oils 
.contain  from  20%  to  25%  saturated  glycerids. 

*  *     * 

To  support  his  theory  of  added  fats,  Dr.  Baskerville  produced  some  charts 
IV,  V  and  VI,  purporting  to  show  how  the  solid  fats  were  increased  in  the 
product  of  the  Burchenal  patent  from  17%  up  to  20  to  25% — but  his  charts,  as 
he  was  forced  to  confess  on  cross-examination,  were  based  upon  the  fundamentally 
wrong  analysis  of  the  cottonseed  oil  given  in  the  patent  in  suit,  and  utterly 
disregarded  the  statement  of  the  patent  that  the  decrease  in  linolin  and  increase 
in  olein  were  what  it  was  desired  to  accomplish.  Dr.  Baskerville  tacitly  ad- 
mitted on  direct  examination,  when  he  presented  his  charts  that  they  were 
illogical. 

*  *     * 

With  Dr.  Baskerville's  admissions  and  concessions,  his  charts  are  swept  into 
the  discard  and  with  them  his  theory  of  "  added  stearin  "  being  the  predom- 
inating feature  of  the  patent  in  suit. 

It  is  self-evident  that  with  the  product  of  the  Burchenal  patent,  being  de- 
scribed in  specific  detail  as  having  20  to  25%  of  saturated  fats,  and  with  cotton- 
,seed  oil  having  20  to  25%  saturated  fats,  there  could  be  practically  no  change 
in  the  proportions  of  the  saturated  glycerids  during  the  hydrogenation.  For 
example,  the  oil  which  Morrison  said  they  were  using  when  he  gave  the  analyses 
of  the  Burchenal  product  had  12.8%  saturated  fats.  The  samples  of  the  average 
product  as  described  in  the  patent  had  23%  saturated  fats.  In  such  case  the 
saturated  fats  were  increased  from  21.8  to  23 — a  difference  of  1.2%. 

Nothing  could  be  clearer,  in  the  patent  in  suit,  than  that  Burchenal  did  not 
want  to  increase  the  stearin,  because  he  thought  it  was  indigestible  and  of 
"  small  value  as  shortening."  What  he  said  he  wanted  to  do,  and  did,  was  to 
have  a  product  with  only  5  to  10%  linolin  and  65  to  75%  olein. 

*  *     * 

Unfortunately  for  Dr.  Baskerville,  he  knew  nothing  of  this  previous  testimony  of 
Mr.  Morrison,  or  he  would  not  have  been  mislead  by  his  zeal  on  plaintiff's  behalf 


690  APPENDIX 

to  advance  such  untenable  theories  as  to  the  patent  in  suit  and  to  back  them  up 
by  his  erroneous  charts. 

*  *    * 

But  in  the  case  at  bar  the  plaintiff  is  seeking  to  exclude  the  public  from  one 
use  of  the  semi-solid  hydrogenized  oil  under  the  claims  sued  on,  though  conceding 
that  the  public  has  the  right  to  it  for  other  uses.  That  is,  by  labeling  it  a 
"  food-product  "  or  calling  it  "  lard-like  "  the  plaintiff  hopes  to  prevent  the  use 
in  cooking,  of  the  product  which  the  public  has  the  right  to  use  in  making  soap, 
or  candles  or  lubricants.  It  is  just  as  though  a  manufacturer  of  hydrogenized 
semi-solid  cottonseed  oil  products  of  a  relatively  soft  consistency,  such  as  that 
of  lard,  should  fill  two  barrels  with  his  product  manufactured  exactly  as  directed 
in  the  patent  in  suit  and  should  label  one  of  them  "  soap  stock  "  and  the  third 
"lard  substitute."  He  ships  the  soap  stock  to  a  soap  dealer  and  he  ships  the 
other  barrel  labeled  "  lard  substitute  "to  a  food  products  jobber.  According  to 
the  plaintiff's  theory  the  original  manufacturer  would  infringe  the  patent  in 
suit  when  he  made  that  part  of  the  hydrogenized  oil  which  he  labeled  as  a  lard 
substitute  and  sold  to  the  food  products  jobber,  and  would  not  infringe  the 
patent  by  marking  the  material  "  soap  stock  "  which  he  shipped  to  the  soap 
maker — a  proposition  which  leads  to  the  inadmissible  conclusion  that  for  one- 
use  or  purpose  the  article  of  manufacture  may  be  public  property  and  for  another 
use  may  be  subject  of  a  patent. 

*  *    * 

So,  while  the  plaintiff  may  have  been  the  first  in  the  United  States  to  hydro- 
genize  oil  for  making  food  products  and  soap  stock  in  accordance  with  the  process, 
which  Kayser  brought  to  this  country,  and  the  first  commercially  to  produce  in 
the  United  States  hydrogenized  fats  for  culinary  and  soap  making  purposes,  it 
really  created  no  new  industry,  but  merely  brought  into  that  old  industry  of 
making  hardened  oil  lard  substitutes,  and  the  old  soap  making  industry,  a 
process  which  was  then  well  known.  The  product  of  the  patent  in  suit,  while  it 
might  have  been  commercially  new  in  the  sense  that  it  was  produced  by  a 
process  which  had  not  actually  been  used  in  this  country  in  producing  like  hard- 
ened cottonseed  oil,  until  Kayser  brought  it  here,  was  not  patentably  novel. 

Moreover,  it  has  not  been  established  that  the  product  of  the  patent  in  suit 
has  ever  been  commercially  manufactured  and  sold.  That  product,  as  has  been 
repeatedly  shown  herein,  must  necessarily  have  not  more  than  10%  linolin,  not 
less  than  65%  olein  and  not  more  than  25%  stearin.  Crisco  was  not  produced 
and  placed  on  the  market  until  May,  1911,  some  six  months  after  the  patent  in 
suit  was  filed,  and  plaintiff's  chemical  superintendent  has  testified  that  it  does 
not  contain  the  proportions  or  percentages  of  the  Component  glycerids  recited 
in  the  patent  as  the  supreme  identifying  test  of  the  patented  product. 

Moreover,  consider  the  enormous  sums  of  money  spent  upon  the  advertising. 
of  Crisco:  Taylor  testified  that  in  1911,  $180,000  was  spent  for  advertising,  and 
$400,000  each  year  thereafter  in  all,— the  vast  sum  of  at  least  $2,000,000  during 
five  years.  That  money  was  spent  in  full  page  or  two  page  advertising  in  all 
the  great  national  and  weekly  magazines;  free  cans  of  Crisco  were  sent  to 
15,000  merchants  selected  throughout  the  United  States;  every  jobbing  dealer 
in  the  United  States  was  supplied  or  furnished  with  advertising  circulars  and 
also  full-size  samples  of  Crisco;  an  extensive  campaign  of  street-car  advertising 
was  carried  out  in  a  dozen  or  more  cities;  bill  poster  and  newspaper  advertising. 


EDIBLE   HYDROGENATED    FATS  691 

was  carried  on;   and  advertising  by  lectures  delivered  in  various  domestic  science 
schools,  and  universities  by  authorities  in  domestic  science. 

Notwithstanding  that  tremendous  and  most  expensive  advertising  campaign, 
the  sales  of  Crisco  at  the  end  of  the  fifth  year  amounted  to  only  one-eighth  to 
one-fourth  of  the  sales  of  another  lard  substitute  made  by  Swift  &  Company, — 
"  Jewel  "  compound  or  shortening. 

The  sales  of  Crisco  therefore  are  not  due  to  any  peculiar  excellence  or  superi- 
ority to  the  product,  but  to  the  campaign  of  advertising.  In  the  present  case, 
the  plaintiff  used  an  attractive  trade-mark  name  "  Crisco "  which  doubtless 
helped  to  make  the  advertising  effective.  Anything,  that  is  not  absolutely 
dangerous,  can  be  sold  in  large  quantities  if  more  than  $2,000,000,  is  spent  in 
advertising  it. 

*    *     * 

An  argument  based  upon  commercial  exploitation  fails,  therefore: 

First,  because  a  new  industry  was  not  created,  but  on  the  contrary  an  old 
process  was  employed  in  an  old  industry  to  produce  an  old  result; 

Second,  because  the  sales  of  Crisco  were  due,  not  to  any  intrinsic  merit  pos- 
sessed by  it,  but  to  a  stupendous  advertising  campaign,  and  the  expenditure  of 
enormous  sums  of  money  in  advocating  and  inducing  its  purchase;  and 

Third,  because  the  sale  of  Crisco  is  no  criterion  as  to  the  novelty  or  utility 
of  the  product  of  the  patent  in  suit,  since  Crisco  does  not  meet  the  supreme 
identifying  test  prescribed  in  the  patent. 


SHORTENING  VALUES 

(a)  The  specification  of  the  patent  says  that  solid  fats  such  as  the  saturated 
glycerides  of  the  fatty  acids,  stearic,  palmitic,  etc.,  "  are  of  very  small  value  for 
shortening,"   lines  46-48,  page   1.     Defendant  has  shown  by  Dr.  Bacon  that  the 
Ward    Baking  Company  now  uses    only  the  hard   fats   having   a   high   melting 
point  as  shortening  in  the  manufacture   of  bread  and  that  a  remarkably  small 
amount    will    suffice    for    the    purpose.     The    McFarland  patent    No.   884,606, 
describes  the  use  of  a  hard  fat  as  a  shortening  agent  as  early  as  April  14,  1908, 
the  date    of  its    issue;    and    the  use    of  stearine,  mixed  with  acid   phosphate,  in 
baking  powders  and  self-raising  flour,  is  described  in  the  Horsford  patent  of  1856, 
quoted  by  Judge  Blatchford  in  Rumford  Chemical  Works  vs.  Lauer. 

Miss  Hanko,  the  plaintiff's  culinary  expert,  testified  that,  as  to  a  hard  fat,, 
such  as  in  Florolene,  in  which  it  is  admixed  with  flour,  she  could  see  no  objec- 
tion to  the  hard  fat  as  a  shortening  agent. 

(b)  The  specification  says  that: 

Oil,  liquid  at  the  ordinary  temperatures,  does  not  make  the  best  short- 
ening, because  the  oil  remains  liquid,  keeping  the  food  in  a  soggy  condi- 
tion, and  the  oil  will  even  settle  to  the  under  part  of  the  cooked  product 
and  soil  the  cloth,  paper,  or  whatever  it  may  come  in  contact  with,  page 
1,  lines  54-61. 

This  statement  has  been  disproved  by  Dr.  Walker,  by  Miss  Hanko,  and 
by  Dr.  Bacon,  the  latter  further  testifying  that  for  many  years  large  bread 
bakeries  used  only  liquid  oil  in  the  manufacture  of  bread  as  the  shortening  agent. 


692  APPENDIX 

(c)  The  specification  states  that: 

It  is  evident,  therefore,  that  oils  or  fats  containing  notable  quantities 
of  glycerides  of  linolic  acid  or  of  lesser  saturation,  are  distinctly  inferior 
as  an  edible  product  to  those  containing  a  minimum  of  these  glycerides 
with  a  larger  per  cent  of  olein,  page  1,  lines  35-41. 

Cottonseed  oil  contains  a  notably  high  percentage  of  linolin  (48%)  whereas 
olive  oil  contains  a  small  percentage — less  than  10%  (see  Walker's  chart,  No.  9) 
— and  about  80%  of  olein,  but  common  usage  as  a  table  oil  shows  that  cotton- 
seed oil  is  not  "  distinctly  inferior "  to  olive  oil.  In  Bulletin  No.  505  of  the 
United  States  Department  of  Agriculture  dated  February  13,  1917,  of  which, 
as  a  publication  of  the  United  States  Government,  this  Court  may  take  judicial 
notice,  it  is  said,  page  18: 

With  allowance  for  metabolic  products,  the  coefficients  of  digestibility 
have  been  found  to  be  for  olive  oil  97.8;  for  cottonseed  oil  97.8;  for 
peanut  oil  98.3;  for  cocoanut  oil  97.9;  for  sesame  oil  98;  and  for  cocoa 
butter  94.9  per  cent.  These  values  indicate  that  the  vegetable  oils  studied, 
with  the  exception  of  cocoa  butter,  have  for  all  practical  purposes  the 
same  digestibility  and  are  utilized  as  completely  as  the  animal  fats." 

(d)  The  specification  contains  an  analysis  of  cottonseed  oil,  which  all  of  the 
experts  agree  is  fundamentally  erroneous,  and  which  was,  as  has  already  been 
shown  herein,   based  on  a  blunder  by   Mr.   Morrison,  who  made  the  analysis. 
This  needs  no  further  elaboration. 

(e)  The   specification   states   in   effect   that   the   product,   having   a   range   in 
iodine  value  of  55  to  80,   contains   "  from  about   1.5%  to  2.5%  of  additional 
hydrogen  more  than  in  the  non-hydrogenized  material,"  page  2,  lines  4  to   7, 
whereas   Mr.   Richter   has   shown   that   a   partially  hydrogenized    cottonseed  oil 
product  with  an  iodine  value  of  80  contains  2.04%  additional  hydrogen  and  that 
a  like  product  with  an  iodine  value  of  55  contains  3.75%  additional  hydrogen, 
more  than  in  the  original  non-hydrogenized  cottonseed  oil.     T.  R.,  pages  603, 
Qsl98-199.     This  was  not  controverted  by  plaintiff  on  rebuttal,  and  shows  that 
the  statement  quoted  from  the  specification  as  to  the  percentage  of  additional 
hydrogen  is  not  founded  on  fact. 

(f)  The  "  puffing  "  or  self -laudatory  statements  of  the  patent  as  to  the  lesser 
liability  of  the  product,   responding  to  the  identifying  tests  of  the  patent,   to 
become  rancid  than  lard,  and  its  capacity  to  be  heated  to  a  higher  temperature 
than  lard,  and  its  being  an  "  ideal "  product  for  frying  and  better  than  lard  as 
a  shortening  are  incapable  of  proof,  and  even   "  Crisco  "  has  not  been  shown 
by  plaintiff  to  excel  in  the  respects  noted.     Defendants  on  the  contrary  have 
shown,   by  Dr.   Bacon,   that  Crisco  turns  rancid  more  rapidly  than  lard,   Dr. 
Bacon,   RDQ363,  T.   R.,  page  722,  and  by  Mr.   Richardson  that  the  smoking 
point  temperatures  of  lard  and  lard  substitutes  depend  upon  the  deodorization 
of  the  products  with  live  steam,  and  that  this  is  true  of  all  fats.     The  steam 
treatment  drives  off  the  volatile  constituents  of  the  fat,  and  raises  the  tempera- 
ture at  which  the  fat  will  begin  to  smoke  when  heated  to  high  temperatures. 
Richardson,  Qs37-43,  T.  R.,  page  558. 


EDIBLE   HYDROGENATED   FATS  693 

DEFENDANT'S  PROCESS  AND  PRODUCT 

Defendant's  product,  Kream  Krisp,  was  first  placed  on  the  market  in  Sep- 
tember, 1914,  and  by  March  1st,  1915,  the  production  was  between  one  and  two 
tons  daily  or  at  an  annual  rate  of  300,000  to  600,000  pounds.  Richter,  pp. 
207-208,  T.  R.,  604,  605.  Kream  Krisp  evidently  came  to  the  attention  of  the 
plaintiff  soon  after  it  was  placed  on  the  market,  since  in  February,  1915,  Burch- 
enal  wrote  to  the  defendant  that  it  was  infringing  its  patents  on  "  food  products  " 
though  in  point  of  fact  he  then  had  no  food  product  patents.  The  application 
for  patent  in  suit  was  pending,  however — so  he  filed  an  amendment  presenting 
present  claims  1  and  2  on  March  5,  1915,  and  lowered  the  melting  point  range, 
as  originally  given,  doubtless  with  the  hope  of  covering  Kream  Krisp. 

Kream  Krisp  is  produced  by  a  wholly  different  process  from  that  described 
in  the  patent  in  suit,  the  process  of  its  manufacture  being  patented  in  Letters 
Patent  to  Hugh  K.  Moore,  No.  1,121,860,  dated  December  22,  1914,  applied  for 
Feb.  26,  1914,  and  No.  1,184,489,  dated  May  23,  1916,  applied  for  Oct.  31, 
1914;  Ex.  Book,  pages  62,  78.  In  the  "batch  process,"  as  described  in  the 
Norman  British  patent,  the  Kayser  patents  and  the  patent  in  suit,  a  batch  of 
oil  with  the  finely  divided  catalyst  mixed  therewith,  is  heated,  and  by  bubbling 
the  hydrogen  through  the  mixture,  or  agitating  the  mixture  in  the  presence  of 
hydrogen,  there  is  caused  a  triple  contact  of  a  small  body  of  catalyst,  a  large 
body  of  oil,  and  hydrogen — in  consequence  of  which  a  certain  "  selective  action  " 
takes  place  and  the  linolin  is  first  acted  on  by  the  hydrogen  and  converted  to 
olein  during  the  early  stages  of  the  process. 

In  the  defendant's  process  the  body  of  nickel  catalyst — not  chemically  de- 
posited on  kieselguhr — but  mechanically  mixed  with  shredded  asbestos,  for  the 
same  purpose  that  hair  is  mixed  with  plaster  to  keep  the  layer  from  cracking, — 
is  spread  in  layers  between  sheets  of  asbestos.  These  layers  form  a  horizontal 
diaphragm  in  the  hydrogenating  vessel.  Then  oil  heated  to  the  desired  tempera- 
ture is  sprayed  by  heated  hydrogen  from  a  rotating  nozzle  arranged  above  the 
diaphragm.  Additional  heated  hydrogen  is  admitted  to  the  vessel,  or  "  capsule  " 
as  it  is  called,  in  the  compartment  above  the  diaphragm,  so  that  the  pressure 
above  the  diaphragm  is  greatly  in  excess  of  that  below  it.  The  fine  spray  of 
oil  is  therefore  instantly  driven  through  the  porous  catalytic  diaphragm,  and 
emerges  therefrom,  a  portion  of  it  being  hydrogenized  in  its  transit.  The  rotating 
nozzle  sprays  the  oil  on  successive  portions  of  the  diaphragm, — the  hydrogen 
alone  sweeping  through  the  other  portions  of  the  diaphragm  and  "  revivifying  " 
the  catalyst  by  the  absorption  of  the  hydrogen  on  the  nickel  particles,  or  by 
uniting  therewith  to  form  an  unstable  hydride.  The  oil  in  passing  through 
the  diaphragm  in  the  twinkling  of  an  eye  is  acted  on  by  the  hydrogen  in  or  on 
the  catalyst — and  since  the  catalyst  is  greatly  in  excess  of  the  oil  which  is  passing 
therethrough — the  selective  action  of  the  batch  process  does  not  take  place. 
On  the  contrary,  a  portion  of  the  linolin  is  converted  directly  to  a  saturated 
glyceride  (stearin)  or  else  coincidently  a  portion  of  the  linolin  is  converted  to 
olein  and  approximately  a  like  portion  of  olein  is  converted  to  stearin.  The  result 
is  that  in  the  product  of  defendant  the  percentage  of  olein  is  substantially  the 
same  as  in  the  original  oil,  while  the  stearin  has  been  increased  at  the  expense 
of  the  linolin.  The  resultant  product  contains  the  same  kind  of  glycerides  as 
the  original  oil  (disregarding  Dr.  Baskerville's  theory  of  mixed  and  simple  glycer- 
ides) but  they  are  in  different  proportions.  Walker,  Qs34-65,  T.  R.,  pages  492- 


694  APPENDIX 

516.  The  cottonseed  oil  which  is  employed  by  defendant,  is  thus  converted 
into  a  product  like  the  sample  can  introduced  in  evidence  by  the  plaintiff,  as 
follows: 

Cottonseed  Oil.  Kream  Krisp. 

Per  cent  saturated  glycerides 31 . 5  28 

Per  cent  olein 32.5  34.3 

Per  cent  linolin 46  37 . 7 

The  range  of  the  proportions  of  component  glycerides  given  by  Mr.  Richter, 
who  has  charge  of  the  analyses  of  Kream  Krisp  at  defendant's  factory,  is  as 
follows : 

Per  cent  saturated  fats 28-43 

Per  cent  olein 34.3-37 

Per  cent  linolin 33.3r37.7 

The  iodine  values  of  Kream  Krisp  range  from  83.8  to  94.7;  the  melting 
points  range  from  33.9°  to  46.6°  C.;  and  the  titers  range  from  33.4  to  36.5. 

In  the  particular  product,  on  which  the  charge  of  infringement  is  based, 
to  wit,  that  contained  in  the  Kream  Krisp  can  be  offered  in  evidence  by  plaintiff 
as  a  part  of  Exhibit  No.  2,  the  melting  point  is  35.7,  the  titer  23.85,  the  sapon- 
ification  value  194.5  and  the  Halphen  test  is  negative.  So  far  as  the  Halphen 
test  is  concerned,  Richter  testified  that  the  sample  was  most  unusual,  since  he 
had  never  before  seen  any  of  defendant's  product  which  did  not  give  a  positive 
result  on  being  tested,  and  explained  that  the  oil  was  probably  overheated. 

On  comparing  the  Kream  Krisp  with  the  original  oil  from  which  it  was  pro- 
duced, it  is  very  striking  that  the  proportion  or  percentage  of  olein  in  the  two 
is  substantially  the  same,  having  been  increased  from  32.5%  in  the  oil  to  34.3% 
in  the  product — an  increase  of  1.8%.  The  linolin  has  been  decreased  from 
46%  to  37.7%  or— 8.3  and  the  stearin  increased  from  21.5  to  28%  or  6.5. 

Cottonseed    Kream 
Oil.  Krisp. 

Saturated  glycerides  21 . 5 +6 . 5  =  28 
Olein  32.5+1.8  =  34.3 

Linolin  46-8.3=37.7 

The  stearin  or  saturated  glycerides  have  been  mainly  increased  at  the  expense 
of  the  linolin.  It  cannot  be  said  of  the  product  that  it  is  "  high  in  olein  " — 
within  the  purview  of  the  patent  in  suit,  because  there  was  substantially  no 
increase  in  the  proportion  of  olein  in  the  original  oil;  nor  can  it  be  said  that 
the  product  is  "  low  in  linolin  "  since  more  than  one-third  of  it  consists  of  lin- 
olin. Only  8.3%  of  the  original  oil  has  been  changed  at  all — 1.8  has  been 
changed  from  linolin  to  olein  and  6.5  has  been  changed  to  stearin. 

The  remainder  of  the  product  has  been  unchanged.  Whether  the  linolin 
was  converted  directly  to  stearin  with  only  a  small  portion  being  converted  to 
olein,  or  whether  with  the  conversion  of  8.2  parts  of  linolin  to  olein,  6.5  parts  of 
olein  is  changed  to  stearin  simultaneously  therewith,  is  not  known,  and  there  is 
at  present  no  known  method  of  analysis  by  which  this  can  be  definitely  ascer- 
tained. 


EDIBLE   HYDROGENATED   FATS  695 


KREAM  KRISP  DOES  NOT  INFRINGE  THE  PATENT  IN  SUIT 

So  far  as  the  proportions  of  the  glycerides  is  concerned  there  is  a  profound 
difference  between  the  two  products — that  of  the  Burchenal  patent  and  Kream 
Krisp — as  might  be  expected  from  the  totally  different  processes  by  which  they 
are  produced.  In  addition,  the  iodine  values  are  different,  the  titers  are  different, 
and  the  percentage  of  added  hydrogen  are  different,  all  as  will  be  seen  from  the 
following  comparison,  using  Richter's  figures: 

Burchenal  Product.  Kream  Krisp. 

Iodine  value 55-80  94.7 

Melting  point 33°-40°  C.          35.7 

Titer 35°-42°  C.  33.85 

Per  cent  saturated  fats 20-25  28 

Per  cent  olein 65-75  34.3 

Per  cent  linolin 5-10  37.7 

Per  cent  added  hydrogen 1.5-2.5  .875 

Saponifi cation  value 195  194 . 5 

It  will  be  noted  from  the  foregoing  that  the  iodine  value  of  Kream  Krisp 
is  94.7  as  against  the  maximum  of  80  given  in  the  patent  in  suit;  that  Kream 
Krisp  contains  more  than  three  times  the  maximum  quantity  of  linolin  stated 
in  said  patent,  contains  a  little  more  than  half  of  the  minimum  quantity  of 
olein,  and  3%  more  than  the  maximum  quantity  of  saturated  fats  or  stearin; 
that  the  titer  is  less  than  the  minimum  given;  and  that  the  per  cent  of  added 
hydrogen  is  less  than  that  given  in  the  patent. 


Kream  Krisp  does  not  meet  a  single  identifying  test  pointed  out  in  the  patent 
in  suit,  with  the  exception  of  its  melting  point,  which  is  given  by  Richter  as 
35.7°  C.;  and  as  to  the  melting  point  be  it  remembered  that  when  Burchenal 
first  filed  his  application  the  melting  point  range  was  then  given  as  from  36 
to  43°  and  years  afterwards  changed  to  33°-40°  because  Burchenal  changed  his 
opinion  as  to  what  the  desirable  melting  point  should  be. 

That  Kream  Krisp  does  not  infringe  the  patent  in  suit  is  thus  made  olear. 

It  is  true  that  Kream  Krisp  is  used  as  a  substitute  for  lard  or  butter,  and  is 
of  such  consistency  that  it  may  be  used  in  their  stead.  In  that  respect  it  does 
not  differ  from  the  lard  substitutes  like  Jewel  and  Flake  White, — in  fact,  it  is 
much  more  like  Jewel  compound  than  it  is  like  the  product  of  the  patent  in  suit. 

We  call  attention  to  a  very  significant  statement  in  the  patent  to  be  found 
in  lines  89-94,  page  1,  thereof,  as  follows: 

In  practice,  the  operation  is  stopped  when  the  oil  has  been  converted 
into  a  product  which  cools  to  a  white  or  yellowish  semi-solid  more  closely 
resembling  lard  than  do  the  commercial  mixtures  of  cottonseed  oil  and  animal 
oleo  stearin.  .  .  .  (Italics  ours.) 

Just  what  the  italicized  clause  means,  the  patent  does  not  state.  It  cannot 
mean  that  it  is  different  from  those  compounds  by  reason  of  the  melting  point, 
or  the  uses  to  which  they  are  respectively  put,  for  therein  lie  no  distinctions. 
It  may  mean  that  the  Burchenal  product  is  chemically  more  like  lard,  inasmuch 
as  lard  has  8%  to  10%  of  linolin  and  is  relatively  high  in  olein.  If  the  latter 


696  APPENDIX 

is  meant,  then  surely  it  excludes  Kream  Krisp,  as  will  be  apparent  by  a  com- 
parison of  Kream  Krisp  with  Jewel  compound,  which  was  one  of  the  commercial 
mixtures  referred  to,  and  the  Burchenal  product. 

Kream  Krisp.  Jewel.  Burchenal  Product. 

Per    cent   saturated    glycerids 28  29.5            20-25 

Per  cent  olein 34.3  29                65-75 

Per  cent  linolin 37.7  41 .5              5-10 

The  comparison  can  best  be  made  visually  by  the  triangular  chart  402  (oppo- 
site page  575,  of  the  Trial  Record),  produced  by  Richter,  on  which  the  products 
are  graphically  portrayed  in  the  terms  of  these  three  components,  to  wit:  sat- 
urated glycerids,  olein  and  linolin  referred  to  in  the  patent  in  suit.  We  here 
reproduce  that  chart  which  Dr.  Baskerville  admits  is  an  "  excellent  "  chart  for 
indicating  the  percentages  of  the  component  glycerids.  The  cottonseed  oil, 
Kream  Krisp,  Jewel  and  Burchenal's  product  are  all  located.  A  mere  glance 
shows  that  Jewel  and  Kream  Krisp  are  quite  similar  in  their  composition,  and 
that  both  are  equally  remote  from  the  composition  of  the  Burchenal  product. 
They  also  have  approximately  the  same  percentages  of  solid  or  saturated  fats, 
although  slightly  more  than  Crisco. 

Kream  Krisp  therefore  is  directly  excluded  from  the  scope  of  the  patent,  in 
addition  to  its  failure  to  meet  the  identifying  tests  which  are  described  in  the 
specification  thereof. 

While,  in  the  production  of  Kream  Krisp,  a  portion  of  the  oil  is  hydrogenized — 
it  is  by  a  process  wholly  different  from  that  described  by  Burchenal.  In  fact, 
the  record  clearly  shows  that  by  the  batch  process  and  under  the  conditions  of 
hydrogenation  recited  in  the  patent  in  suit  Kream  Krisp  cannot  be  produced; 
and  that  by  the  process  practiced  by  defendant  it  is  impossible  to  produce  the 
product  described  and  denned  in  the  patent. 


The  patent  in  suit  was  pending  in  the  Patent  Office  five  years,  during  which 
the  art  progressed,  and  defendant's  product  had  appeared  on  the  market.  After 
the  application  for  patent  was  filed  on  November  10,  1910,  and  was  rejected 
by  the  Examiner  on  December  13,  1910,  Burchenal  deliberately  let  the  matter 
lay  for  one  year  until  December  13,  1911,  before  replying  to  the  examiner.  The 
case  was  promptly  rejected  again  on  December  29,  1911,  and  again  nearly  eleven 
months  passed  by  before  Burchenal  responded  on  November  20,  1912.  In  the 
meantime  Ellis  had  secured  patent  No.  1,038,545  for  a  butter  substitute,  and 
then  Burchenal  tried  to  claim  that  his  material  was  a  butter  substitute  also. 
Burchenal,  however,  had  described  his  material  as  melting  from  36°  to  43°  C., 
that  is,  at  a  temperature  higher  than  36.6°  C.  (blood  heat),  whereas  a  vital 
characteristic  of  butter  is  that  it  melts  below  blood  heat  or  body  temperature, 
It  was  at  this  time  that  Burchenal  presented  the  matter  occurring  in  lines  13  to 
74,  page  1,  of  his  printed  specification,  except  that  in  line  64  he  then  referred  to 
his  product  as  "  butter-like "  instead  of  "  lard-like."  Burchenal  was  trying  to 
grab  Ellis'  invention. 

The  Examiner  however  prevented  that,  refusing  to  permit  Burchenal  to  call 
his  product  "  butter-like "  and  pointing  out  that  the  preferred  melting  point 
as  originally  described  by  Burchenal,  was  41°-42°  C.,  and  that  it  was  very  much 
higher  than  the  melting  point  of  butter.  Foiled  in  his  attempt  to  cover  the 


EDIBLE   HYDROGENATED   FATS  697 

Ellis  product,  Burchenal  then  concluded  that  his  own  material  was  "  lard-like  " 
and  inserted  that  expression  for  the  first  time  in  his  claims.  Later  on,  March  17, 
1913,  Burchenal  took  out  of  his  claims  reference  to  the  melting  point  of  36°  to 
43°  C.  and  substituted  a  reference  to  the  iodine  value  instead.  This  was  evi- 
dently done,  because  he  wanted  to  get  rid  of  that  high  melting  point  range  of 
"  36°  to  43°  C."  in  his  specification,  and  it  was  his  first  move  in  that  direction. 
He  accomplished  his  ultimate  purpose  on  March  5,  1915,  when  he  substituted  in 
his  present  specification  a  statement  giving  the  melting  point  range  from  33° 
to  40°,  thus  changing  what  he  had  originally  sworn  was  one  of  the  identifying 
tests  of  his  product.  As  Morrison  testified,  Burchenal  probably  "  changed 
his  opinion  afterwards  "  as  to  the  preferred  melting  point  of  his  product. 


CONCLUSION 

Without  attempting  to  summarize  all  the  matters  discussed  in  the  brief, — 
for  the  length  of  which  we  apologize — we  submit  that  we  have,  by  the  Record 
in  this  case,  established  beyond  a  shadow  of  doubt  the  several  defenses  set  up 
in  the  answer  as  amended. 

I.  We  have  proved  that  prior  to  any  date  of  invention  that  can  be  claimed 
for  Burchenal,  the  hydrogenation  of  the  various  animal  and  vegetable  oils  to 
various  degrees  of  saturation,  or  to  various  consistencies,  had  been  explained 
fully,  clearly  and  exactly  by  Normann,  Bedford,  Paal  and  Roth,  Fokin  and 
Kayser;  that  the  phenomena  of  the  reaction  had  been  so  minutely  described 
that  any  oil  chemist  or  technologist  was  able  to  reproduce  the  processes  and 
reproduce  the  products,  as  was  actually  done  by  witnesses  called  by  the  defend- 
ant; that  the  earlier  patentees  and  investigators  had  called  attention  to  the 
freedom  from  rancidity  which  the  hydrogenized  products  possessed,  to  their 
failure  to  respond  to  the  Halphen  reaction,  to  the  various  iodine  values  and 
consistencies  which  could  be  secured  in  the  products,  and  to  the  fact  that  in  the 
process  no  side  reaction  products  were  produced  save  nickel-soap,  which  was 
easily  removable  by  known  methods;  and  in  fact  that  their  various  products  were 
edible  food  products. 

We  have  proved  by  the  admissions  and  concessions  of  Burchenal,  patentee  of 
the  patent  in  suit,  that  he  was  not  the  originator  of  the  process  of  hydrogenation 
described  in  said  patent;  and  that  he  makes  no  claim  to  the  process,  or  any 
part  thereof,  described  in  the  two  Kayser  patents,  which  process,  as  accurately 
and  exactly  described  in  one  of  the  Kayser  patents,  is  for  hydrogenating  cotton- 
seed oil  to  a  semi-solid  of  any  desired  consistency  as  determined  by  its  iodine 
value  or  titer;  that  such  process  was  disclosed  to  him  (Burchenal)  by  Kayser; 
and  that,  in  fact  Kayser's  products  were  edible  including  those  brought  to  this 
country  by  Kayser. 

We  have  further  shown  that  Kayser  disclosed  to  Von  Phul,  a  disinterested 
witness,  that  he  was  working  on  a  food  product,  and  that  he  showed  the  first 
material  produced  by  him  in  this  country  to  Von  Phul  and  told  the  latter  it  was 
his  new  food  product,  and  this  before  Burchenal  by  "  cerebration  "  decided  that 
Kayser's  products  were  edible;  we  have  shown  that  Kayser  himself  is  not  and 
was  not  available  as  a  witness,  and  therefore  could  not  be  called  to  substantiate 
Von  Phul's  evidence;  and  we  have  shown  that  we  have  called,  as  hostile  wit- 


698  APPENDIX' 

nesses,  the  only  persons  who  did  know  of  Kayser's  work,  namely,  Burchenal, 
Anderson  and  Procter,  whose  testimony  would  naturally  be  biased  on  behalf  of 
the  plaintiff. 

We  have  proved  that  Burchenal  was  not  an  independent  inventor — that  he 
was  not  one  skilled  either  in  the  art  of  hydrogenation  or  in  the  art  of  fatty  food 
products,  that  he  could  point  to  no  single  inventive  act  or  deed  that  could  be 
credited  to  him,  and  that  his  knowledge  touching  the  production  of  semi-solid 
hydrogenized  cottonseed  oil  was  all  obtained  from  Kayser — the  fountain  head  of 
his  information. 

We  have  proved,  by  the  very  records  of  the  plaintiff,  the  production  by 
Kayser  on  March  5,  1908,  of  a  semi-solid  incompletely  hydrogenized  cottonseed 
oil  having  the  melting  points  42°  and  43°  C.,  one  of  which  Burchenal  described 
in  his  application  as  filed  as  the  preferred  melting  point  of  his  patented  product 
which  Kayser  products  were  reproduced  for  the  trial  and  were  shown  by  Mr. 
Richter  to  be  edible. 

These  facts  established  the  invalidity  of  the  patent  for  want  of  originality, 
novelty,  and  lack  of  patentable  invention. 

II.  We  have  shown  that  the  description  contained  in  the  specification  and 
the  claims  in  suit  are  lacking  in  that  completeness,  clarity,  and  exactness  which 
U.  S.  R.  S.,  4888  requires  as  a  condition  precedent  to  the  grant  of  letters  patent, 
for  we  have  proved  both  by  the  concessions  and  admissions  of  Burchenal  and 
Anderson  that  it  would  be  "  a  lucky  strike  "  if  one  should  produce  the  alleged 
new  product  by  following  the  description  contained  in  the  specification,  and  by 
the  testimony  of  Richter  that  he  failed  after  repeated  trials  and  experiments — 
following    the    description    of    the    patent — to   realize  the   alleged   new   product 
having  the  proportions  of  component  glycerides  stated  therein. 

We  have  proved  by  BurchenaPs  concession  that  even  he  does  not  know  what 
factors  are  necessary  to  produce  a  partially  hydrogenated  semi-solid  cottonseed 
oil  which  is  high  in  olein  and  low  in  linolin  with  only  sufficient  stearin  to  make 
the  product  congeal,  as  defined  in  the  specification,  which  the  patent  states  is 
chief  characteristic  of  the  alleged  new  product. 

These  facts  as  proven  establish  that  the  patent  is  void. 

III.  We  have  established  out  of  the  mouths  of  the  plaintiff's  officers,  including 
the  patentee  himself,  that  if  there  be  any  invention  in  the  patent  in  suit  (which 
we  have  shown  is  not  so)  it  is  the  invention  of  Kayser,  and  that  taking  advan- 
tage of  Kayser's  absence  from  this  country  Burchenal  patented  the  same.     The 
facts  as  proven  show  that  this  was  done  unjustly  and  surreptitiously. 

Wherefore,  the  patent  in  suit  is  void. 

IV.  We  have  proved  by  the  proceedings  in  the  Patent  Office  in  connection 
with  the  filing  and  prosecution  of  the  patent  in  suit,  and  by  the  admissions  of 
the  patentee,  and  the  limitations  imposed  by  the  Commissioner  acting  through 
the  Examiner  that  the  alleged  new  product  is  necessarily  limited  lo,  and  must 
contain,  a  specific  percentage  of  component  glycerides,  to  wit:   20-25%  saturated 
glycerides,  65-75%  olein,   and  5-10%  linolin,  in  addition  to  falling  within  an 
iodine  value  range  of  55  to  80,  and  that  no  product  can  infringe  the  claims  of 
the  patent  which  does  not  meet  both  these  identifying  tests. 

V.  We  have  proved  that  new  matter  vitally  changing  the  original  description, 
and  which  was  not  predicated  upon  the  original  disclosure,  and  which  was  a 
radical   departure  therefrom,   was  inserted  in  the  specification  without   a  sup- 
plemental oath,  and  that  the  claims  in  suit  were  inserted  without  a  supplemental 


EDIBLE   HYDROGENATED    FATS  699 

oath  after  defendant's  product  was  in  public  use  and  on  sale,  by  virtue  of  all  of 
which  the  patent  and  said  claims  are  invalid. 

VI.  We    have    proved   that    the   manufacture    of   homogeneous   lardlike    food 
products  consisting  of  cottonseed  oil  hardened  to  the  consistency  of  lard,  is  an 
old  and  well-known  industry;    that  giving  to  the  oil  its  semi-solidity  (1)  by  par- 
tial hydrogenation,  (2)  by  the  addition  of  hard  hydrogenized  fats,  or  (3)  by  the 
addition  of  the  usual  oleo  stearine,  enables  it  in  either  case  to  be  used  for  all 
purposes  as  a  substitute  for  lard  in  the  culinary  arts  and  for  food  purposes,  and 
that  in  the  last  analysis   (as  distinguished  from  a  product  having  the  propor- 
tions of  component  glycerides  recited  in  the  patent),  the  amount  of  added  solid 
fat  is  substantially  the  same,  as  conceded  by  Mr.  Morrison,  plaintiff's  chemical 
superintendent.     Hence,  when  the  plaintiff  makes  the  claim  that  it  has  started 
a  new  industry,  it  can  only  mean  that  it  has  extended  into  an  old  industry  an 
old  product  produced  by  an  old  process.     In  this  connection  we  have  shown 
that  "  Crisco,"  which  the  plaintiff  relies  on  as  the  product  of  the  patent  in  suit, 
is  not  in  reality  that  product,  as  it  fails  to  meet  the  supreme  identifying  test  of 
the  patent,  i.e.,  the  proportions  of  percentage  of  component  glycerids.     And  we 
have  further  shown  that  no  one  but  the  plaintiff  really  knows  just  how  Crisco 
is  made,  and  just  what  processes-  are  used  in  its  production.     "  Jealously  guarded  " 
secrets  constitute  a  wall  around  Crisco,   through  whose  unpenetrable  thickness 
neither  the  Court  nor  this  defendant  nor  the  public  can  see  to  learn  the  real 
process  of  its  manufacture.     And  we  have  further  shown  that  millions  of  money 
have  been  lavished  with  a  free  hand  to  force  Crisco  on  the  public,  in  every  way 
known    to    advertising    managers,    including    the    subsidizing    of    cooking    school 
and  university  lectures.     Yet,  notwithstanding  the  spending  of  fortunes  rivalling 
the  lavish  outlays  of  the  Count  of  Monte  Cristo,  the  annual  sales  of  Crisco  are 
less  one-fourth  than  those  of   "  Jewel "   shortening  manufacturing  by  one  con- 
cern— Swift  &  Co. 

VII.  By  the  record  we  have  proved: 

(a)  That  defendant's  product  does  not  meet  the  identifying  tests  set 
forth  in  the  patent  in  suit,  since  it  has  neither  the  titer,  the  iodine  value, 
the  saponification  value,  nor  the  proportions  or  percentages  of  component 
glycerids,  therein  set  forth  as  identifying  the  alleged  new  product. 

(b)  That  defendant's  product  is  not  "  lard-like  "  in  the  sense  in  which 
those  words  are  used  in  the  patent  and  that  it  neither  smells  nor  tastes 
like  lard,  both  the  taste  and  smell  thereof  being  different  from  the  char- 
acteristic taste  and  smell  of  lard. 

(c)  That  defendant's  product  is  not  made  by  the  process  described  in 
the  patent  in  suit. 

(d)  That  the  process  as  described  in  the  patent  in  suit  will  not  produce 
defendant's  product. 

(e)  That  defendant's  process  is  a  process  covered  by  the  Moore  patents 
and  is  clearly  unlike  the  process  of  the  patent  in  suit,  and  that  the  reac- 
tions   in    the    two    processes    proceed    differently    and    produce    markedly 
different  results,  and 

(f)  That  defendant's  process  cannot  produce  the  product  of  the  patent  in 
suit.     Therefore,  the  defendant's  product  does  not  infringe  the  patent  in  suit. 


700  APPENDIX 

VIII.  We  have  shown  in  addition  to  the  foregoing,  that  the  equities  in  the- 
case  at  bar  are  with  the  defendant;  that  its  product  is  directly  excluded  from 
the  scope  of  the  patent  in  suit  by  the  specification — since  its  chemical  composi- 
tion is  substantially  that  of  "  commercial  mixtures  of  cottonseed  oil  and  animal 
oleo-stearin  "  from  which  the  patented  product  is  distinguished  in  the  specifica- 
tion; that  it  embarked  upon  the  manufacture  of  its  product  in  good  faith; 
that  the  claims  in  suit,  unsupported  by  a  supplemental  oath,  were  deliberately 
inserted  in  the  application  after  defendant's  product  had  for  months  been  pro- 
duced in  large  quantities  and  had  gone  into  public  use  and  had  been  inspected 
by  the  patentee. 

We  urge  that  the  Court,  in  the  protection  of  the  rights  of  the  public  and  of 
this  defendant,  should  declare  this  patent  in  suit  to  be  invalid  or  void,  and  thus 
preserve  to  the  public  and  the  defendant  the  inherent  right  to  put  to  their 
natural  uses  those  hydrogenized  oils  which  it  is  conceded  the  patentee  did  not 
invent  or  discover. 

And  we  urge  that  the  Court  should  also  find  as  a  matter  of  both  fact  and  law 
that  defendant's  product  "  Kream  Krisp  "  is  not  an  infringement  of  the  patent 
in  suit. 

We  submit  that  on  the  grounds  stated  the  bill  should  be  dismissed  with  costs 
in  favor  of  the  defendant. 

Respectfully  submitted, 

MARCUS   B.   MAY, 
JOHN  C.   PENNIE, 

Counsel  for  Defendant. 

New  York,  N.  Y.,  April  28,  1917. 


THE  DECISION  OF  JUDGE  AUGUSTUS  N.  HAND. 

This  suit  is  for  infringement  of  patent  No.  1,135,351,  granted  to  the  com- 
plainant as  assignee  of  John  J.  Burchenal,  on  April  13th,  1915.  The  applica- 
tion for  the  patent  was  filed  November  10th,  1910.  The  specification  states 
that  the  invention  is  for  a  food  product  consisting  of  a  vegetable  oil,  preferably 
cottonseed  oil,  partially  hydrogenized  and  hardened  to  a  homogeneous  white  or 
yellowish  semi-solid  closely  simulating  lard. 

Claims  1  and  2  alone  are  in  issue  and  read  as  follows: 

1.  A  homogeneous  lard-like  food  product  consisting  of  an  incompletely 
hydrogenized  vegetable  oil. 

2.  A    homogeneous    lard-like    food    product    consisting    of   incompletely 
hydrogenized  cotton-seed  oil. 

The  special  object  of  the  invention  is,  according  to  the  specification: 

...  to  provide  a  new  food  product  for  a  shortening  in  cooking  in 
which  the  liability  to  become  rancid  is  minimized  and  in  which  the  com- 
ponents of  such  vegetable  oils  which  are  inferior  and  detrimental  to  use 
as  such  a  food  product  have  been  to  a  large  extent  converted  into  a 
higher  and  more  wholesome  form.  All  such  vegetable  oils  contain  gly- 
cerids  of  unsaturated  fatty  acids  and  among  these  notable  quantities 


EDIBLE   HYDROGENATED    FATS  701 

of  fatty  glycerids  of  lower  saturation  than  olein.  It  is  the  presence  of 
these  glycerids  of  lower  saturation  that  seriously  affects  the  rancidity  of 
the  material.  Oxidation  is  largely  the  cause  of  rancidity  which  oxidation 
weakens  the  fat  at  the  point  of  absorption  at  the  double  bonds,  and  these 
glycerids  of  lesser  saturation  readily  absorb  oxygen  from  the  air  at  ordinary 
temperatures  while  the  more  highly  saturated  glycerids,  as  olein,  only 
absorb  oxygen  at  elevated  temperatures.  It  is  evident,  therefore,  that 
oils  or  fats  containing  notable  quantities  of  glycerids  of  linolic  acid  or  of 
lesser  saturation  are  distinctly  inferior  as  an  edible  product  to  those  con- 
taining a  minimum  of  these  glycerids  with  a  larger  per  cent,  of  olein. 
On  the  other  hand  while  it  is  important  to  get  rid  of  the  readily  oxidizable 
glycerids  of  lower  saturation,  it  is  also  important  not  to  supply  too  large 
a  per  cent,  of  fully  saturated  glycerids. 

...  In  manufacturing  this  product  cottonseed  or  other  vegetable  oil 
is  caused  to  chemically  absorb  a  limited  amount  of  hydrogen  by  reacting 
on  the  oil  with  hydrogen  in  the  presence  of  a  catalytic  agent  and  at  an 
elevated  temperature.  The  oil  is  preferably  agitated  in  a  closed  vessel 
in  the  presence  of  an  atmosphere  of  compressed  hydrogen,  a  catalyzer 
of  finely-divided  nickel  carried  by  kieselguhr  being  maintained  in  sus- 
pension in  the  oil  and  its  temperature  being  raised  to  about  155°  C. 

According  to  the  present  invention,  the  amount  of  hydrogen  absorbed 
is  carefully  regulated  and  limited.  In  practice,  the  operation  is  stopped 
when  the  oil  has  been  converted  into  a  product  which  cools  to  a  white 
or  yellowish  semi-solid  more  closely  resembling  lard  than  do  the  com- 
mercial mixtures  of  cottonseed  oil  and  animal  oleo-stearin  while  in  many 
respects  the  product  is  superior  to  the  best  leaf  lard  as  a  shortening.  It 
is  not  so  liable  to  become  rancid  and  the  product  can  be  heated  to  a 
considerably  higher  temperature  than  lard  without  smoking  or  burning. 
The  high  temperature  to  which  my  product  can  be  raised  without  smoking 
or  burning  makes  the  product  ideal  for  frying,  inasmuch  as  a  crust  forms 
almost  instantly  on  the  food  fried,  which  prevents  any  absorption  of  the 
shortening.  A  lard-like  product  thus  prepared  from  cottonseed  oil  has  a 
saponification  value  of  about  195  and  an  iodin  value  ranging  from  about 
55  to  about  80.  The  product  having  an  iodin  value  of  55  has  a  titer  of 
about  42°  and  a  melting  point  of  about  40°  C.,  that  having  an  iodin 
value  of  80  has  a  titer  of  about  35°  and  a  melting  point  of  about  33°  C. 
While  but  partially  hydrogenized,  containing  from  about  1.5%  to  2.5% 
of  additional  hydrogen  more  than  in  the  non-hydrogenized  material,  it 
shows  no  free  cottonseed  oil  when  subjected  to  the  Halphen  test,  thereby 
differing  from  all  commercial  lard  substitutes  containing  this  oil.  It 
contains  from  twenty  to  twenty-five  per  cent  of  fully  saturated  glycerids, 
from  five  to  ten  per  cent  linolin,  and  from  sixty-five  to  seventy-five  per 
cent  olein;  and  an  average  of  a  number  of  samples  gives  twenty-three 
per  cent  of  saturated  fats,  seven  and  five-tenths  per  cent  linolin  and 
sixty-nine  and  five-tenths  per  cent  olein,  while  the  cottonseed  oil  before 
treatment  contained  seventeen  per  cent  saturated  fats,  thirty-seven  per 
cent  linolin  and  forty-six  per  cent  olein.  It  will  thus  be  seen  that  I  have 
produced  an  ideal  food  product  which  is  high  in  olein,  low  in  linolin  and 
lesser  saturated  fats  and  with  only  enough  stearin  to  make  the  product 
congeal  at  ordinary  temperatures. 


702  APPENDIX 

The  complainant  urges  that  Burchenal  first  taught  the  art  that  a  partially 
hydrogenated  vegetable  oil,  preferably  cottonseed  oil,  was  edible  and  was  a 
useful  lard  substitute.  It  contends  that  prior  to  Burchenal's  conception  it  was 
not  known  that  hydrogenated  cottonseed  oil  was  edible  and  that  the  only 
processes  then  in  use  aimed  at  complete  saturation  and  produced  a  hard  non- 
edible  product.  Before  discussing  the  prior  art,  I  would  say  in  general  that 
Normann,  whose  patent  will  later  be  referred  to,  had  already  disclosed  a  method 
of  hydrogenating  oils,  and  had  set  forth  in  his  specification  that  the  process  was 
progressive  and  involved  "  no  secondary  reaction."  The  method  of  adding 
cottonseed  oil  to  beef  stearin  for  use  as  a  lard  compound  was  well  known  and 
much  used,  as  it  still  is.  The  hydrogenation  of  cottonseed  oil  resulted  in  a 
reduction  of  the  fluid  and  substitution  of  the  solid  fats.  Normann's  patent,  as 
well  as  various  experiments  of  scientists,  indicated  that  the  addition  of  hydrogen 
to  cottonseed  oil  would  result  in  the  reduction  or  elimination  of  the  fluid  and 
substitution  of  solid  or  partially  solid  fats.  No  one  has  shown  that  the  product 
resulting  from  such  hydrogenation  was  ever  non-edible  or  unsanitary  in  any 
respect. 

The  British  patent  No.  10,783  (1887),  to  Joseph  Sears  was  for  a  lard  substitute 
composed  of  refined  unbleached  cottonseed  oil  and  a  fat  adapted  to  give  a  stiff- 
ness to  the  compound  corresponding  substantially  to  that  of  refined  lard.  The 
specification  provided  that  the  temperature  should  be  raised  sufficiently  to  melt 
the  fat  or  stearin,  the  heated  ingredients  mixed  and  then  chilled  rapidly  so  as  to 
prevent  crystallization  and  separation.  This  general  process  was  well  known  in 
the  art  before  the  date  claimed  for  the  invention  of  Burchenal  and  indeed  is 
referred  to  in  the  patent  in  suit.  A  very  large  market  for  such  lard-like  com- 
pounds exists  at  the  present  time  and  has  existed  many  years  past. 

The  British  patent  No.  1515  of  1903,  to  Normann  discloses  a  process  for  the 
reduction  of  glycerides  resembling  that  of  the  patent  to  Burchenal.  Normann's 
patent  says  that: 

The  property  of  finely-divided  platinum  to  exercise  a  catalytic  action 
with  hydrogen  ...  is  already  known.  .  .  .  Recently  Sabatier  and  Sen- 
derens  of  Paris  have  discovered  that  other  finely-divided  metals  will  also 
exercise  a  catalytic  effect  on  hydrogen,  viz.:  iron,  cobalt,  copper  and  espe- 
cially nickel. 

By  causing  acetylene,  ethylene  or  benzene  vapour  in  mixture  with 
hydrogen  gas  to  pass  over  one  of  the  said  metals  (which  had  just  been 
reduced  in  a  current  of  hydrogen)  the  said  investigators  obtained  from 
the  unsaturated  hydrocarbons,  saturated  hydrocarbons,  partly  with  simul- 
taneous condensation. 

I  have  found  that  by  this  catalytic  method  it  is  easy  to  convert  unsat- 
urated fatty  acids  into  saturated  acids. 

This  may  be  effected  by  causing  fatty  acid  vapours  together  with 
hydrogen  to  pass  over  the  catalytic  metal,  which  is  preferably  distributed 
over  a  suitable  support  such  as  pumice  stone.  It  is  sufficient,  however, 
to  expose  the  fat  or  the  fatty  acid  in  a  liquid  condition  to  the  action  of 
hydrogen  and  the  catalytic  substance. 

For  instance,  if  fine  nickel  powder  obtained  by  reduction  in  a  hydrogen 
current,  is  added  to  chemically  pure  oleic  acid,  the  latter  heated  over  an 
oil  bath  and  a  strong  current  of  hydrogen  is  caused  to  pass  through  it 


EDIBLE   HYDROGENATED   FATS  703 

for  a  considerable  time,  the  oleic  acid  may  be  completely  converted  inta 
stearic  acid. 

The  quantity  of  the  nickel  thus  added  and  the  temperature  are  imma- 
terial and  will  only  affect  the  duration  of  the  process.  Apart  from  the 
formation  of  small  quantities  of  nickel  soap,  which  may  be  easily  decom- 
posed by  dilute  mineral  acids,  the  reaction  passes  off  without  any  secon- 
dary reaction.  The  same  nickel  may  be  used  repeatedly.  Instead  of 
pure  oleic  acid,  commercial  fatty  acids  may  be  treated  in  the  same  man- 
ner. The  fatty  acid  of  tallow  which  melts  between  44  and  48°  C.  has  an 
iodine  number  35.1  and  a  yellow  colour  will  after  hydrogenation  melt  be- 
tween 56.5  and  59°,  while  its  iodine  number  is  98  and  its  colour  slightly 
lighter  than  before,  and  it  will  be  very  hard. 

The  same  method  is  applicable  not  only  to  free  fatty  acids,  but  also 
to  the  glycerines  occurring  in  nature,  that  is  to  say,  the  fats  and  oils. 
Olive  oil  will  yield  a  hard  tallow-like  mass;  linseed  oil  and  fish  oil  will  give 
similar  results. 

By  the  new  method  all  kinds  of  unsaturated  fatty  acids  and  their 
glycerides  may  be  easily  hydrogenized. 

The  Normann  patent  clearly  discloses  that  oils  may  be  completely  hydro- 
genized, that  the  process  is  progressive  and  that  it  involves  "  no  secondary 
reaction,"  in  other  words,  that  cotton  seed  oil  which  starts  edible  remains  so. 
The  experiments  and  articles  of  Paal  and  Roth,  which  were  alluded  to  at  the 
trial,  show  that  hydrogenization  of  oils  including  cotton  seed  oil  was  under- 
stood in  the  prior  art. 

Such  being  the  state  of  the  art,  Edwin  Cuno  Kayser  wrote  Procter  &  Gamble 
from  England  that  he  had  a  process  of  considerable  value  and  would  like  to  talk 
to  them  about  it;  thereafter  he  came  to  America  about  November,  1907,  bringing 
samples  of  hydrogenized  cottonseed  oil.  He  showed  these  to  Burchenal,  the 
superintendent  of  Procter  &  Gamble.  As  a  result  of  his  visit,  he  made  an 
arrangement  under  a  preliminary  contract  of  January,  1908,  to  experiment  upon 
the  hydrogenized  cottonseed  oil  as  a  substitute  for  lard.  The  first  project  was 
apparently  to  use  hydrogenated  cottonseed  oil  as  a  compound  to  be  added  to  a- 
percentage  of  beef  stearin  and  cottonseed  oil.  Burchenal  says  he  had  done  no 
work  in  connection  with  hydrogenizing  cottonseed  oil  before  he  saw  Kayser. 
He  testified  that: 

Mr.  Kayser  went  out  to  our  factory  and  made  sketches  as  to  the  appa- 
ratus that  would  be  necessary  to  carry  on  this  work  and  the  apparatus 
was  ordered  at  once;  a  little  plant  was  installed  for  experimental  pur- 
poses and  I  think  it  was  ready  to  operate  sometime  in  January  or  Feb- 
ruary, 1908.  Deposition  of  Burchenal,  page  11. 

The  defendant  succeeded  in  obtaining  contemporaneous  memoranda  as  to  some 
of  Kayser's  experiments  from  the  records  of  Procter  &  Gamble.  The  first  experi- 
ment was  as  follows: 

Fat  Hardening  Process  by  E.  C.  Kayser. 

First  experimental  lot  was  completed  Jan.  17th,  1908.  Fat  treated — 
Summer  Yellow  Cotton-seed  Oil.  Used  nickel  Sulphate  and  Kieselguhr 
as  described.  Experiment  was  conducted  by  Mr.  Kayser  alone.  He 
claims  to  have  used  about  1%  Nickel  Metal  and  2%  Kieselguhr. 


704  APPENDIX 

M.P.  of  fat  after  3  hrs.  55£°  C. 

M.P.  of  fat  after  6£  hrs.  60.3°  C. 

Dr.  Bender  reports  as  follows: 

Melting  point  of  fat  60.3°  C. 

Hydrocarbons  .33%.  * 

Iodine  value  of  fat  7.14%. 

The  fat  does  not  contain  free  fatty  acids.  This  material  is  much  supe- 
rior to  the  samples  from  J.  Crossfield  &  Sons  which  showed  an  iodine 
value  of  52.26  and  a  melting  point  of  39.3°  C.  (The  laboratory  sample 
melted  at  49.9°  C.)  Their  samples  contained  5.12%  free  fatty  acids  and 
2%  hydrocarbons. 

Mr.  Kayser  reports  as  follows:  "  The  melting  point  of  fatty  acid,  pre- 
pared from  first  lot  hardened  cottonseed  oil  is  62°  C.  This  is  several 
points  higher  than  I  ever  got  before.  Presumably  the  composition  of 
your  oil  differs  somewhat  from  that  of  the  oil  I  handled  formerly." 

Another  experiment  by  Kayser  of  the  date  of  March  5,  1908,  was  also  obtained 
from  the  Procter  &  Gamble  records  in  which  the  following  melting  points  ap- 


5  hrs.  at  ordinary  pressure  42°  C. 
1£  hrs.  at  60  Ib.  pressure  43°  C. 


Von  Phul  testified  that  Kayser  told  him  in  1907  that  he  was  getting  up  a 
patent  for  a  food  product  and  even  Burchenal's  own  testimony  shows  that 
Kayser  supposed  that  the  product  he  was  making  was  edible.  If  Kayser  at 
first  told  him  it  was  not  edible  he  did  so  when  they  were  negotiating  and  he 
wished  to  keep  his  process  in  the  dark  until  he  had  arranged  his  terms.  That 
Kayser's  statement  that  it  was  not  edible  was  not  taken  seriously  by  either 
party  is  shown  by  the  following  testimony: 

Q887.  But  you  did  not  know  as  a  matter  of  fact  whether  it  would  be 
edible  or  not?  A.  I  did  not.  Mr.  Kayser  stated  that  it  would  not  be 
but  that  was  his  method  of  talking. 

Both  of  these  men  were  proceeding  soon  after  Kayser's  arrival  in  this  country 
to  develop  hydrogenated  cottonseed  oil  as  a  food  product.  Even  if  the  thought 
first  occurred  to  Burchenal  I  cannot  see  that  he  did  anything  to  carry  it  out  in 
practice.  Kayser's  patent  No.  1,003,035,  application  for  which  was  filed  March 
20,  1908,  disclosed  the  process  which  was  employed  to  make  the  product  covered 
by  the  patent  in  suit,  and  the  specification  for  this  Kayser  patent  contains  the 
statement  that  "  The  time  of  treatment  will  vary  with  the  progress  realized  and 
with  the  degree  of  saturation  aimed  at."  It  is  to  be  remembered  that  Burchenal 
distinctly  disclaimed  in  his  testimony  that  he  had  anything  to  do  with  the 
invention  of  the  process  covered  by  the  Kayser  patents  and  we  thus  have  a 
situation  where  Kayser  invented  the  process  and  developed  the  product  to  the 
point  where  it  was  applicable  to  use  as  a  food  product.  He  came  to  America 
with  a  sample  which  as  appears  from  the  written  record  taken  from  the  files  of 
the  complainant  had  a  melting  point  of  only  39°  and  developed  other  samples 
with  melting  points  of  but  42°  and  43°  in  his  March  5,  1908  experiments. 


EDIBLE   HYDROGENATED   FATS  705 

Moreover,  it  is  to  be  remembered  that  Crosfield  had  employed  Kayser  to 
experiment  in  hydrogenating  oil,  that  the  former  had  been  in  close  communica- 
tion with  Normann,  who  had  patented  only  four  years  before  the  process  I  have 
mentioned,  and  that  Crossfield  had  so  strenuously  objected  to  the  use  by  Procter 
&  Gamble  of  the  processes  of  Kayser  that  they  were  obliged  to  purchase  their 
rights  to  them.  It  is  also  noteworthy  that  Kayser  refused  to  testify  in  this  case 
and  that  the  witnesses  as  to  the  work  of  Kayser  in  America  are  officers  or  em- 
ployees of  the  complainant.  Under  such  circumstances  the  meagerness  of  the 
evidence  which  has  been  adduced  to  show  that  Burchenal  had  anything  to  do 
with  the  development  of  the  lard-like  food  product  which  is  the  subject  of  the 
patent  in  suit,  coupled  with  his  admission  that  the  entire  process  under  which  it 
was  made  was  the  work  of  Kayser,  is  most  significant  and  makes  it  impossible 
to  find  that  Burchenal  invented  anything.  The  defendant  has  been  embarrassed 
in  its  defence  by  many  difficulties  and  has  been  obliged  to  go  into  the  enemy's 
camp  to  secure  almost  all  its  ammunition.  In  spite  of  this,  it  has  established 
that  Kayser  at  the  very  beginning  had  developed  not  only  a  process  but  a 
product  little  differing  from  Crisco.  Kayser  remained  with  Procter  &  Gamble 
until  well  into  1910,  and  did  not  leave  America  until  about  July  of  that  year. 
While  there  is  some  general  evidence  of  what  Burchenal  and  others  did,  or  di- 
rected, I  can  find  no  real  proof  that  anyone  but  Kayser  did  anything  of  sub- 
stantial moment.  No  step  was  taken  by  Burchenal  that  could  possibly  amount 
to  invention. 

Complainant  urges  that  the  experiments  of  Kayser  and  the  patents  of  Nor- 
mann and  Kayser  aimed  at  complete  saturation  and  that  neither  realized  the 
importance  of  a  partially  hydrogenized  product.  But  the  process  under  which 
their  products  were  made  involved  in  its  progress  partial  hydrogenation,  and 
Kayser's  patent  No.  1,004,035  distinctly  stated  that  "  The  time  of  treatment 
will  vary  with  the  progress  realized  and  with  the  degree  of  saturation  aimed  at." 
Kayser  as  far  as  I  can  see  did  everything  that  was  done  to  develop  Crisco,  and 
if  his  work  fell  short  of  this,  he  achieved  enough  so  that  the  final  step  was  inev- 
itable to  one  skilled  in  the  art.  Kayser's  process  was  the  complainant's  process 
and  his  product  involved  a  progressive  reaction  fitted  for  any  purpose.  The 
broad  discovery  as  between  him  and  Burchenal  certainly  belongs  to  him. 

Furthermore  under  any  fair  interpretation  of  the  patent  there  is  no  infringe- 
ment. The  file  wrapper  indicates  that  the  examiner  rejected  the  claims  as 
originally  filed  saying: 

...  If  the  problem  of  simulating  lard  from  cotton-seed  oil  were  pre- 
sented to  an  oil  chemist,  an  incomplete  hydrogenization  of  the  cotton- 
seed oil  would  at  once  suggest  itself  to  him  as  a  solution  of  the  problem. 
All  the  claims  are  accordingly  rejected  on  the  .  .  .  ground  of  lack  of 
invention. 

Thereafter  new  claims  were  rejected  upon  the  Kayser  patents  for  the  reason 
that  his  process  could  be  arrested  at  any  time  to  produce  an  incompletely  hydro- 
genized product.  Then  and  for  the  first  time  Burchenal  filed  an  amendment 
setting  forth  certain  percentages  of  linolin,  olein  and  stearin  which  his  product 
should  contain.  It  seems  quite  evident  therefore  that  Claims  1  and  2  of  his 
patent  would  under  such  circumstances,  if  valid  at  all,  be  limited  to  substantially 
the  chemical  composition  described  in  the  amended  specification.  Indeed  the 
specification  closes  with  the  statement  that  the  inventor  has  produced  a  product 


706 


APPENDIX 


which  "  is  high  in  olein,  low  in  linolin  and  lesser  saturated  fats  and  witii  only 
fcnough  stearin  to  make  the  product  congeal  at  ordinary  temperatures." 

Under  such  circumstances  it  is  impossible  to  treat  the  melting  point  as  prac- 
tically the  determining  factor  and  if  this  is  not  done  the  defendant's  product 
Kream  Krisp  does  not  infringe.  After  the  examiner  had  held  that  an  incomplete 
hydrogenation  would  suggest  itself  to  any  chemist  seeking  to  simulate  lard  and 
rejected  the  claims  on  Kayser,  the  patentee  as  I  have  shown,  amended  by  speci- 
fying a  particular  product  and  dwelling  upon  the  advantages  of  a  small  percent- 
age of  linolin  to  avoid  rancidity.  If,  therefore,  the  inventor  contributed  anything 
to  the  art  it  was  this  special  chemical  composition  which  his  patent  discloses. 
Claims  1  and  2  should  consequently  be  construed  in  the  tight  of  the  proceedings  of 
Burchenal  before  the  Patent  Office  and  not  given  a  scope  which  would  monopo- 
lize an  art  in  which  Normann,  Kayser  and  others  had  been  the  real  pioneers. 

Kream  Krisp  has  a  chemical  composition  extremely  remote  from  that  described 
in  the  specification  of  Burchenal.  The  following  are  the  relative  percentages: 

Burchenal.  Kream  Krisp. 
Per  cent  saturated  fats  20-25  28 

Per  cent  olein  65-75  34.3 

Per  cent  linolin  5-10  37.7 

Thus  it  appears  that  Kream  Krisp  instead  of  being  low  in  linolin  is  extremely 
high,  and  that  instead  of  being  high  in  olein  as  specified  in  the  Burchenal  patent, 
it  has  a  percentage  of  olein  which  differs  but  little  from  that  existing  in  refined 
cottonseed  oil  unhydrogenated.  In  fact  Kream  Krisp  seems  to  present  many 
of  the  objections  referred  to  in  Burchenal's  specification  and  to  lack  the  very 
things  upon  which  the  latter  based  his  right  to  receive  a  patent.  Indeed  the 
composition  is  much  closer  to  the  lard  compound  Jewel,  made  out  of  stearin  and 
cottonseed  oil  than  to  Crisco. 

The  bill  should  be  dismissed  with  costs  because  the  patent  is  void  for  lack 
of  invention  and  for.  the  further  reason  that  claims  1  and  2  if  properly  construed 
are  not  infringed  by  the  defendant. 

Dated,  October  3,  1917.  A.  N.  H.,  D.  J. 


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EDIBLE  HYDROGENATED  FATS 


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In  commenting  on  the  decision  by  Judge  Hand  in  the  Crisco 
case,  the  American  Food  Journal  (October  1917,  567)  states: 

'This  decision  has  the  effect  of  throwing  open  to  the  food  industry  the  right 
to  make  a  product  similar  to  Crisco,  provided  that  in  so  doing  the  manufacturer 
does  not  infringe  the  process  patent  of  E.  C.  Kayser. 

Some  few  years  ago,  owing  to  the  rapidly  increasing  cost  of  oleostearin,  all 
manufacturers  who  dealt  therein  were  anxiously  casting  about  for  some  less 
expensive  substitute  therefor.  The  practice  of  producing  semi-solid  compounds 
made  by  mixing  soft  oils  with  those  of  stiffer  consistency  was  in  vogue  in  many 
lines,  both  industrial  and  edible,  and  was  recognized  as  a  part  of  the  existent 
art.  The  Kayser  patent,  under  which  Crisco  is  made,  concerns  itself  with  the 
method  by  which  hydrogen  is  made  to  combine  with  oleic  acid  to  form  stearic 
acid,  the  resultant  product  possessing  the  characteristics  of  the  saturated  fatty 
acid  series — less  liability  to  turn  rancid  and  stiffer  consistency. 

The  Burchenal  patent  was  an  attempt  on  the  part  of  Procter  &  Gamble  to 
maintain  all  the  rights  of  a  patentee  as  to  the  finished  product,  irrespective 
of  its  method  of  production. 

The  importance  of  the  suit  is  readily  appreciated  when  it  is  realized  that 
should  the  Burchenal  patent  have  been  upheld,  it  would  have  tended  to  stop 
all  inventive  work  looking  toward  the  production  of  a  product  similar  to  Crisca 
but  made  in  different  fashion.  While  the  courts  are  generally  loath  to  recog- 
nize "  product  patents "  on  the  ground  of  their  being  against  public  policy, 
they  are,  at  all  times,  inclined  to  maintain  the  integrity  of  "  process  patents/' 
the  distinction  being  very  vividly  brought  out  in  the  present  case. 


708  APPENDIX 


BURCHENAL  PATENT  SUSTAINED  ON  APPEAL 

On  appeal,  the  Court  found  the  Burchenal  patent  was  valid  and  infringed  (Judge 
Hough  and  Rogers  concurring,  Judge  Ward  dissenting).  The  opinion,  written  by 
Judge  Hough,  reversing  the  decision  of  the  lower  Court  states  in  part, — The  patent 
law  does  not  speak  in  terms  of  science,  though  scientific  evidence  is  necessary  for  the 
application  of  its  rules.  The  chemical  composition  of  steam,  water  and  ice  is  the 
same,  but  they  are  different  things,  and  in  the  same  commonsense  way,  oil,  lard 
and  stearin  are  different  things,  although  (with  some  chemical  latitude),  the  oil 
may  be  said  ultimately  to  become  stearin,  and  to  pass  through  the  lard  stage  on  the 
way. 

It  may  be  assumed  as  true  that  by  the  mixture  of  cottonseed  oil  and  animal 
stearin,  a  substance  can  be  produced  which,  for  practical  purposes,  is  the  same 
thing  as  Burchenal's  chemically  changed  cottonseed  oil;  but  one  is  a  mixture  and  the 
other  is  not,  and,  assuming  the  difference  to  be  important  from  the  standpoint  of 
either  chemist  or  cook,  it  is  a  vital  difference  from  that  of  the  law. 

We  are,  therefore,  of  opinion  that  there  was  invention  in  Burchenal's  disclosure. 
Product  patents  may  be  justly  subjected  to  critical  scrutiny,  but  these  claims  are 
far  within  the  border  line  adverted  to  in  Fonseca  vs.  Suarez,  232  Fed.  Rep.,  155; 
and,  just  as  the  conversion  of  an  abandoned  machine  into  an  operative  and  suc- 
cessful one  by  the  introduction  of  new,  but  simple  feature  constitutes  invention, 
so  we  think  that  seizing  upon  thing  A,  which  has  been  thing  B,  and  was  to  become 
thing  C,  and  utilizing  the  half-made  but  different  product  amounted  to  an  invention 
which  is  duly,  set  forth  in  this  application. 

The  finding  below,  that  Burchenal  was  not  the  inventor  of  whatever  invention  is 
revealed,  is  really  a  declaration  that  one  Kayzer  did  the  inventing,  and  Burchenal, 
for  some  inexplicable  reason  appropriated  it.  This  is  an  affirmative  defence  and 
must  be  sustained  by  a  fair  preponderence  of  credible  evidence.  Burchenal  swore 
to  invention  in  the  statutory  form,  and  the  presumption  of  validity  extends  to  the 
identity  of  the  inventor,  for  certainly  nothing  could  be  more  completely  invalid  than 
a  patent  for  invention  to  one  who  invented  nothing 


We  are  satisfied  of  the  truth  (entirely  apart  from  all  presumptions)  of  defendants' 
testimony  that  it  was  not  until  Kayzer  had  returned  to  England,  or  was  on  the  point 
of  going,  that  it  occurred  to  anyone  that  it  was  not  necessary  to  first  harden  by 
hydrogenic  saturation  the  cottonseed  oil  and  then  mix  it  with  the  fluid  article  in 
order  to  make  a  lard-like  compound — but  that  the  hardening  process  might  be 
arrested  in  the  manner  and  for  the  purposes  disclosed  by  Burchenal's  application. 

Assuming  now  that  this  mental  operation  or  discovery  in  the  sense  of  the  patent 
law  amounted  to  invention,  we  not  only  find  no  evidence  that  Burchenal  was  not 
the  inventor,  but  it  is  a  strain  upon  credulity  to  believe  that  when  this  plaintiff  cor- 
poration might  just  as  well  have  advanced  an  application  in  Kayzer 's  name  it  delib- 
erately preferred  the  fraud  of  prosecuting  it  in  that  of  Burchenal. 

It  may  be,  and  we  think  is,  quite  true  that  the  evidence  reveals  Burchenal  as 
not  primarily  a  chemist,  but  a  man  of  business  deeply  interested  in  the  advancement 
of  his  corporation's  prosperity.  We  recognize  the  fact  that  there  is  a  fundamental 
difference  between  "new  articles  of  manufacture  and  new  articles  of  commerce"; 
and  it  may  also  be  quite  true  that  Burchenal's  contribution  to  the  sum  of  human 


EDIBLE  HYDROGENATED  FATS  709 

knowledge  grew  out  of  the  trained  business  man's  observation  of  the  possibilities  of 
a  chemist's  process,  which  he  was  himself  quite  incapable  of  devising. 

But  just  as  it  is  immaterial  whether  a  patentee  "understands  or  correctly  states 
the  theory  or  philosophy  of  the  mechanism  which  produces"  his  new  result,  so  it  is 
immaterial  whether,  when  Burchenal  observed  and  seized  upon  as  a  new  and  useful 
thing  a  half  hydrogenically  saturated  oil,  he  was  actuated  rather  by  commercial 
instinct  than  acquired  chemical  knowledge.  It  is  enough  that  he  had  both  a  mental 
conception  and  a  tangible  reduction  to  practice,  and  that  is  all  that  the  patent  law 
requires.  Quite  possibly  this  patentee  would  never  have  conceived  the  thought, 
had  he  not  watched  Kayzer,  but  he  could  and  did  get  something  out  of  Kayzer's 
train  of  phenomena,  which  the  latter  neither  thought  of,  nor  reduced  to  practice. 

The  final  objection  to  a  decree  in  plaintiff's  favor  is  that  properly  construed  the 
claims  in  suit  are  not  infringed  because  (a)  the  defendant's  product  widely  varies 
from  that  of  the  patent  in  the  relative  percentages  of  saturated  fats,  olein  and  lin- 
olin,  (6)  the  process  pursued  by  defendant  in  making  its  product  differs  radically 
from  that  said  to  be  disclosed  or  assumed  in  the  patent  in  suit,  and  (c)  that  said 
claims  are  to  be  regarded  as  strictly  limited,  if  not  substantially  abandoned,  through 
or  by  reason  of  the  proceedings  in  the  Patent  Office  as  revealed  by  file  wrapper  con- 
tents. 

As  to  the  first  point  (a)  it  is  enough  to  note  that,  while  the  variation  insisted  upon 
is  true,  it  must,  to  negative  infringement,  be  at  least  a  variation  extending  beyond 
the  limits  of  a  valid  claim  read  in  the  light  of  the  disclosure. 

In  this  instance  it  is  not  denied  that  what  the  defendant  makes  and  sells  is  not 
only  lard-like,  homogeneous  in  the  sense  of  mixtureless,  and  wholly  consisting  of  an 
incompletely  hydrogenized  cottonseed  oil,  but  it  is  within  the  limits  of  iodin-value, 
titre  and  melting  points  specified  in  the  application.  Therefore,  it  is  an  infringement. 

It  is  true  (6)  that  defendant's  process  of  manufacture  is  very  different  from  that 
of  plaintiff,  and  we  are  willing  to  assume  it  different  from  and  better  than  anything 
known  to  Burchenal  or  developed  by  Kayzer.  But  this  patent  is  upon  a  product, 
and,  if  the  product  complained  of  is  the  patented  article  substantially  as  described, 
it  makes  no  difference  by  what  path  or  process,  new  or  old,  inferior  or  improved,  the 
infringing  product  is  manufactured. 


For  the  reasons  stated  the  decree  appealed  from  is  reversed  with  costs  both  here 
and  below,  and  the  cause  remanded  with  directions  to  enter  a  decree  adjudging 
Claim  1  and  2  valid  and  infringed. 

Judge  Ward,  in  expressing  a  dissenting  opinion,  stated  that  he  considered  the 
District  Judge  right  in  holding  the  patent  void  for  lack  of  invention.  To  apply 
semi-solid  hydrogenized  oil  as  a  substitute  for  lard  in  cooking  was  no  doubt  novel 
and  useful,  but  was  not,  in  his  opinion,  invention.  To  one  skilled  in  chemical  art 
such  use  was  as  obvious  as  were  the  many  mechanical  improvements,  which,  though 
new  and  useful,  have  been  held  not  inventions  within  the  capacity  of  those  skilled 
in  the  art. 

There  was  nothing  revolutionary  about  this  new  use.  Fats  satisfactory  for 
culinary  needs  are  abundantly  available,  yet  the  complainant  is  given  a  monopoly 
of  all  semi-solid  homogeneous  hydrogenized  vegetable  oils,  however  produced, 
when  applied  to  culinary  purposes. 


INDEX 


Abderhalden,  310. 

Abegg,  267. 

Abel,  108. 

Abelous,  248. 

Aboulenc,  114,  220. 

Absorption    of    carbon    monoxide    by 

chemical  agents,  467. 
Absorption  of  gases  by  liquids,  600. 
Absorption  of  hydrogen  by  nickel,  60. 
Absorption  of  hydrogen  by  oil,  23. 
Absorption  of  hydrogen,  rate  of,  71. 
Acceleration  of  catalysis,  194. 
Acetaldehyde,  382. 
Acetanilid,  220,  222. 
Acetate,  benzyl,  376. 
Acetate,  ethyl,  530. 
Acetate,  nickel,  130,  138,  139,  147,  179 

183,  194,  198,  437. 
Acetates,  47,  108,  125. 
Acetic  acid,  salts  of,  130. 
Acetin  method,  313. 
Acetone,  67,  423,  443. 
Acetylene,  112,  260,  422,  471,  532,  534, 

595,  606,  611,  613,  621. 
Acetylene  decomposition,  473. 
Acetyl  number,  284,  295,  381. 
Acetyl  value,  101,349. 
Acid,  acetic,  280,  419,  423. 
Acid,  aconitic,  280. 
Acid,  arachidic,  285.  286. 
Acid,  behenic,  285,  315,  440. 
Acid,  carbonic,  251. 
Acid,  chloric,  273. 
Acid,  cinnamic,  260. 
Acid,  clupanodonic,  360,  440. 
Acid,  ela3omargaric,  401. 
Acid  electrolyte,  558,  562. 
Acid,  erucic,  280,  285,  315,  440. 
Acid,  fatty,  52,  67,  68,  83,  325,  363,  370, 

373,  377,  379,  380,  394,  398,405,  408. 


Acid,  formic,  39,  140,  251. 

Acid,  free  fatty,  324,  351. 

Acid-free  machine  tallow,  358. 

Acid,  hydrocyanic,  247. 

Acid,  hydrofluosilicic,  256. 

Acid,  hydroxy,  313. 

Acid,  hydroxystearic,  440. 

Acid,  hypogeic,  380. 

Acid,  iso-oleic,  379. 

Acid,  linoleic,  89,  280,  380,  439. 

Acid,  linolenic,  280,  325,  380,  439. 

Acid,  linolic,  345. 

Acid,  lysalbinic,  245. 

Acid,  mineral,  443. 

Acid,  naphthenic,  402. 

Acid  number,  288,  292,  294,  295,  304, 
314,379,381. 

Acid,  number  of  hardened  castor  oil,  284. 

Acid,  oleic,  1,  12,  27,  29,  128,  147,  184, 
214,  215,  218,  223,  239,  242,  244,  248, 
250,  275,  280,  297,  325,  326,  340,  398, 
439,  617. 

Acid,  oxystearic,  439. 

Acid,  palmitic,  83,  326,  378,  379. 

Acid-phosphate,  344. 

Acid,  piperinic,  270. 

Acid,  protalbinic,  245. 

Acid-resistant  form  of  colloidal  plati- 
num, 246. 

Acid,  ricinoleic,  280,  439,  440. 

Acid,  silicic,  262. 

Acid,  sludge,  83. 

Acid-stable  protective  colloid,  246. 

Acid,  stearic,  12,  83,  220,  223,  242,  275, 
285,  298,  300,  325,  326,  360,  378,  379, 
398,  408. 

Acid,  sulphuric,  109. 

Acid,  sulphuric,  effect  of  carbonyl,  231. 

Acid,  tartaric,  122,  200. 

Acid,  titanic,  262. 


711 


712 


INDEX 


Acid,  tungstic,  262. 

Acid,  unsaturated,  755,  279. 

Acid,  unsaturated  fatty,  285. 

Acid  values  of  sodium  acid   sulphate, 

method  of  utilizing,  517. 
Acidity,  change  in,  101. 
Acids  on  metals,  action  of,  515. 
Acrolein,  372,  381. 
Activated  aluminum,  595. 
Activation  of  charcoal,  150. 
Activation  of  palladium,  268. 
Activators,  155. 

Activators  for  copper  catalyst,  195. 
Active  carbon,  21. 
Activity  of  catalyzer,  23. 
Activity  of  metals,  275. 
Activity  of  nickel,  270. 
Activity  of  occluded  hydrogen,  275. 
Adam,  60. 
Adamla,  283. 
Adams,  387. 
Adam's  apparatus,  60. 
Addition  of  hydrogen  to  fatty  oils,  282. 
Addition  of  oxygen  to  fatty  oil,  282. 
Adhesion  of  resulting  soap,  prevention 

of,  370. 

Adsorption,  272. 
Aeration  of  fat,  331. 
Aeronautics,  hydrogen  for,  534. 
Agde,  218,  221. 
Agitation,  102. 

Agitation  by  Arnold's  apparatus,  81. 
Agitation  during  hydrogen ation,  620, 626. 
Agitation,  effect  of,  26,  82,  99. 
Agulhon,  108. 
Aigner,  558. 

Air,  effect  on  catalyzer,  110. 
Air  in  hydrogen,  592. 
Albright,  255,  306. 
Albumen,  350. 
Albumin,  118. 
Albumin  in  oils,  109. 
Alcohol,  67,  271,  423. 
Alcohol,  amyl,  86. 
Alcohol,  denatured,  408. 
Alcohol  ethyl,  86. 
Alcohol,  fatty,  284. 
Alcohol  in  soap,  376. 
Alcohol,  octodecyl,  284. 
Alcohol  vapor,  210. 


Aldehyde,  205,  271,  332,  423. 

Aldehydic  impurities,  219. 

Alkaloids,  reduction  of,  246. 

Alkali  ferrite,  458. 

Alkali  refining,  162. 

Allbright-Nell  Co.,  321. 

Allen,  630. 

Allotropic  condition,  273. 

Allotropic  form  of  natural  stearine,  292. 

Alloy  of  nickel  and  cobalt,  95. 

Alloys,  hydrogen  absorption,  278. 

Alloys,  steel,  529. 

Allylacetic  acid,  280. 

Allyl  isothiocyanate,  255. 

Allylmalonic  acid,  280. 

Almond  oil,  301,  310,  658. 

Alpha  benzildioxime,  296. 

Altmayer,  271. 

Alumina,  111,  117,  150,  151,  167,  168, 

171,  173,  192,  195,  254,  262,  348,  428. 
Aluminate  silicate,  260. 
Aluminate,  sodium,  176. 
Aluminum,  151,  161,  246,  248,  267,  421, 

422,  437,  499,  502,  519,  522. 
Aluminum  acetate,  152. 
Aluminum  activated,  595. 
Aluminum,  activation  of,  532. 
Aluminum  and  caustic  soda,  532,  595. 
Aluminum  borate,  155. 
Aluminum  boride,  144. 
Aluminum  chloride  use  on  oils,  329. 
Aluminum  chloride,  418,  425. 
Aluminum  hydrate,  192,  262. 
Aluminum  nitrate,  153,  452,  455. 
Aluminum  oxide,  119. 
Aluminum  phosphate,  152. 
Aluminum  powder,  523. 
Aluminum  silicate,  187,  429. 
Aluminum  silicide,  520. 
Aluminum  silicofluoride,  156. 
Aluminum  sodium  silicide,  519. 
Aluminum  sulphate,  153,  263. 
Aluminum  under  pressure,  effect  of,  419. 
Aluminum,  zinc,  tin,  alloy,  525. 
Alundum,  192,  531. 
Amalgam,  sodium,  273. 
Amalgamation,  532. 
Amalgamated  electrolyzer,  558. 
Amberger,  6,  252,  253,  255,  261,  306,. 

318,  337. 


INDEX 


ria 


American  Cotton  Oil  Company,  334. 
American  Food  Journal,  707. 
American  Leather  Chemists  Association, 

405. 

American  Linseed  Co.,  387. 
American  Oxhydric  Company,  547. 
Amicrons,  218. 
Amines,  84,  165,  168. 
Aminophenol,  8. 

Ammonia,  169,  251,  254,  259,  433,  532. 
Ammonia  and  fatty  acid,  84. 
Ammonia  for  reduction,  171. 
Ammonia,  oxidation  of,  256. 
Ammoniacal  cuprous  chloride  solution, 

599. 

Ammonium  borate,  84,  191. 
Ammonium  chloride  for  reduction,  171. 
Ammonium  chromate,  455. 
Ammonium  phosphate,  155. 
Ammonium  selenite,  155. 
Ammonium  zeolite,  261. 
Amorphous  carbon,  274. 
Amorphous  palladium,  272. 
Amount  of  catalyzer,  99. 
Amyl  alcohol,  86. 
Amyl  oleate,  91. 
Amylene,  116. 
Analcime,  261. 

Analyses  of  hardened  oils,  325. 
Analytical    constants    of   hydrogenated 

oil,  281. 
Analytical  determination  of  free  nickel, 

203. 

Andelite,  363. 
Andersen,  106. 
Anderson,  314,  662,  671,  672. 
Andrew,  269. 
Anethole,  86. 

Anhydrides,  formation  of,  285. 
Anhydrous  alumina,  262. 
Anhydrous  nickel  oxide,  114. 
Anhydrous    oxides     and     hydrates   of 

nickel,  116. 
Anilides,  84,  91. 
Aniline,  91,  107,  153,  248,  614. 
Aniline  and  oleic  acid,  91. 
Animal  charcoal,  249. 
Animal  fats,  hydrogenated,  242,  333. 
Animal  oils,  hardened,  372. 
Anode,  cobalt,  577. 


Anode,  platinum,  280. 

Anode,  zinc,  274. 

Anthracene,  220,  222. 

Anti-catalytic  action  of  certain  metals, 

248. 

Anti-catalytic  bodies,  effect  of,  249. 
Anti-catalytic  substances,  see  catalyzer 

poisons. 

Antimony,  246,  265,  455. 
Antimony  bromide,  164. 
Aouara,  402. 
Apparatus  for  circulation  of  hydrogen 

gas,  26. 

Apparatus  for  extraction  of  nickel,  234. 
Apparatus  for  hydrogen  at  high  pressure, 

529. 
Apparatus  for  laboratory  hydrogenation,. 

76. 
Apparatus  for  making  catalytic  material,. 

157. 
Apparatus  for  reducing  metallic  oxides, 

156. 
Apparatus  for  separating  hydrogen  from 

other  constituents  of  water  gas,  465. 
Apparatus,  hydrogenation,  414. 
Apparatus  of  Arnold,  81. 
Apparatus  of  Charlton,  62. 
Apparatus  of  Chisholm,  57. 
Apparatus  of  de  Jahn,  68. 
Apparatus  of  Hemptinne,  31. 
Apparatus  of  Higgins,  95. 
Apparatus  of  Hoehn,  82. 
Apparatus  of  Humphreys,  64. 
Apparatus  of  Ittner,  93. 
Apparatus  of  Sugita,  93. 
Apparatus  of  Voswinckel,  52. 
Apparatus,  reduction,  171. 
Application  of  electricity,  3. 
Arabic,  gum,  200. 
Arachidic  acid,  285,  286,  299,  309,  314r 

345. 

Arachidic   acid   in   hydrogenated   men- 
haden oil,  299. 

Arc  decomposition  of  water,  558. 
Arc,  iron,  62. 
Arc  method,  245. 
Arc  on  petroleum  oils,  419. 
Arc  process,  142. 
Ardery,  534. 
Ardol,  Ltd.,  603. 


714 


INDEX 


Armitage,  400. 

Armour  &  Co.,  357. 

Arnold,  81. 

Aromatic  amines,  168. 

Aromatic  compounds,  246. 

Aromatic  compounds  by  dehydrogena- 
tion,  434; 

Aromatic  hydrocarbons,  426. 

Aromatic  hydrocarbons  as  solvents,  96. 

Aromatic  hydrocarbons  from  coal,  437. 

Aromatic  substances,  222. 

Aromatic  sulpho-fatty  acids,  398. 

Arsenic,  153,  232,  254,  443,  596,  609. 

Arsenic  as  a  poison,  14. 

Arsenic  in  hydrogen,  163. 

Arsenic  oxide,  164. 

Arseniuretted  hydrogen,  609. 

Arseniuretted  hydrogen,  removal  of,  596 

Artificial  geranium  oil,  376. 

Artificial  lard,  354. 

Asbestos,  56,  67,  133,  135,  139,  171,  174, 
190,  198,  239,  251,  252,  254,  259,  391, 
404,  420,  432,  449,  485,  693. 

Asbestos  cloth  partition,  537. 

Asbestos,  diaphragm,  559,  560,  563,  565, 
570,  578,  581,  584,  589,  591. 

Asbestos,  nickelized,  12. 

Asbestos,  nickel  on,  391. 

Asche,  356. 

Ash.  395. 

Ash,  content  of,  327. 

Ash  of  hardened  oil,  305. 

Ash  of  hydrogcnated  oil,  361. 

Ash  of  oil,  295. 

Ashe,  341. 

Asp  bock,  60. 

Asphalt,  420. 

Assimilation  of  fats,  326. 

Astbury,  614. 

Atack,  296. 

Atkinson,  343. 

Atomization,  cathode,  74. 

Atomization  of  hydrogenated  oil,  342. 

Atomizing  process,  13. 

Auerbach,  267,  324,  359. 

Aufrecht,  294. 

Autoclave  treatment,  371. 

Automatic  control  of  Burdett  appara- 
tus, 563. 

Automatic  control,  system  of,  585. 


Bacon,  176,  423,  481,  646,  656,  691. 

Bacteria  free  whale  oil,  330. 

Badische  Co.,  52, 152,  168,  173, 175,  254, 

256,  259,  423,  449,  451,  453,  455,  469, 

476,  498,  499,  529,  596,  599. 
Baffle  plate  system,  95. 
Baillio,  530. 
Baker,  421. 
Baku  oil,  424. 
Baku  petroleum,  258. 
Ballantyne,  615,  623. 
Ballingall,  508. 
Balloons,    inflation   of   with   hydrogen, 

533. 

Bamberger,  520. 
Bancroft,  166. 
Barbe,  79. 

Barium  chlorate,  273. 
Barium  chloride,  250,  257. 
Barium  chromate,  155. 
Barium  hydrate,  458. 
Barium  nitrate,  155. 
Barium  oxide,  152. 
Barium  sulphate,  526,  534. 
Barium  sulphide,  535. 
Barium  tungstate,  155. 
Barnes,  85. 
Barnitz,  107. 
Bartels,  9,  124,  128,  183,  211,  215,  220, 

226. 

Barth,  559. 
Barth  system,  483. 
Barth  vaporisation  chamber,  483. 
Barton  system,  515. 
Barus,  443. 
Baryta,  428. 
Base  metals  as  catalyzers,  108,  118,  146, 

172,  199. 
Basic  compounds  as  catalyzer  formative 

material,  129. 

Basic  nickel  carbonate,  98,  224,  225. 
Basic  oleate  of  copper,  196. 
Baskerville,  95,  140,  167,  637,  638,  641, 

667,  670,  671,  689. 
Bassano,  85. 
Batch  methods,  643. 
Batch  process,  693. 
Baudouin  reaction,  242. 
Baudouin  test,  309,  325. 
Bauer,  86. 


INDEX 


715 


Bauxite,  428. 

Becchi  &  Halphen  reaction,  242. 

Becchi  method,  205. 

Becchi  test,  285,  309,  638. 

Bedford,  8,  12,  13,  19,  50,  51,  89,  108, 
109,  118,  120,  121,  122,  123,  128,  130, 
133,  138,  199,  203,  208,  209,  210,  211, 
220,  222,  224,  292,  400,  406,  465,  643, 
657,  697. 

Bedford's  apparatus,  51. 

Bedford-Erdmann  Process,  126. 

Beef  fat,  355. 

Beef  tallow,  289,  309,  325,  365,  371. 

Beeswax,  hydrogen  from,  473. 

Behenic  acid,  285,  298,  314,  315,  440. 

Beketoff,  276. 

Bell-collector  type  of  generator,  556. 

Bellier's  reaction,  309. 

Bellucci,  138,  204. 

Belou,  500. 

Belting,  408. 

Benker,  556. 

Bennie,  519. 

Benzaldehyde,  reducing  effect  of,  205. 

Benzene,  67,  160,  424,  426,  430,  431, 
438,  621.  See  also  Benzol. 

Benzene  from  petroleum,  422. 

Benzildioxime,  296. 

Benzine,  419,  423. 

Benzine-xylene,  292. 

Benzoate,  nickel,  186. 

Benzol,  see  also  Benzene. 

Benzol,  419,  424,  434. 

Benzol,  carbonyl  in,  233. 

Benzol  extraction  of  catalyzer,  214. 

Benzol  for  degreasing,  219. 

Benzol,  hydrogenation  of,  270. 

Benzol  ring,  175. 

Benzyl  acetate,  376. 

Benzyl  oleate,  91. 

Bequevort,  517. 

Bergen,  249. 

Bergius,  79,  106,  256,  339,  431,  513,  519. 

Bergius  high-pressure  process,  527. 

Bergo,  371,  386. 

Berlin  Mills  Co.,  644,  650. 

Berlin-Anhaltische  Maschinenbau,  A.  G., 

.   474,  476,  500,  599. 

Berlin-Anhaltische  Maschinenbau,  A.G., 
Process  of,  514. 


Bernegau,  357. 

Berthelot,  230,  231,  232. 

Beryllium,  455. 

Beryllium  oxide,  152. 

Beta-naphthol,  220. 

Bettendorf  plant,  570. 

Bianchi,  294. 

Biazzo,  315,  316. 

Bichromate  method,  313. 

Bilheimer,  280. 

Billwiller,  431. 

Bipolar  electrode  generator,  588. 

Bipolar  electrodes,  541. 

Bipolar  generator,  571. 

Birkeland,  36,  72,  419. 

Bismuth,  246,  248,  265. 

Bisulphide,  carbon,   15,  160,  165,  318, 

443. 

Bitter  almond  oil,  377. 
Bitumen,  hydrogen  from,  473. 
Black,  palladium,  5,  11. 
Blankenhorn,  107. 
Blankit,  388. 
Bleaching  oils,  61. 
Blended  hydrogenated  oil,  344. 
Blue  chamomile  oil,  256. 
Blum,  107,  440. 
Boberg,  120,  142. 
Baking  powder  and  hydrogenated  fat, 

343. 

Bock,  49,  60,  520. 

Boehringer  &  Soehne,  5,  106,  210,  244. 
Boeseken,  101,  260,  280. 
Bog  iron  ore,  511. 
Bohm,  119,  125,  328,  329,  382. 
Bomer,  283,  288,  289,  291,  324,  325,  443. 
Bomer  method,  308. 
Bond  ethylene,  271. 
Bone  fat,  364,  386. 
Bontoux,  339,  398,  534. 
Borate,  154,  178,  525. 
Borate,  aluminum,  155. 
Borate,  ammonia,  84. 
Borate,  ammonium,  191. 
Borate,  calcium,  191. 
Borate,  nickel,  179,  207. 
Boric  acid,  154,  520. 
Boride,  aluminum,  144. 
Boride,  nickel,  186. 
Borneol,  106,  128. 


716 


INDEX 


Boron,  152. 

Boron  as  catalyzer,  143. 

Boron,  calcium  fluoride,  156. 

Boron  hydride,  143. 

Bosch,  155,  190,  451,  454,  473,  598,  600. 

Bosch  hydrogen  producer,  509. 

Bosshard,  184,  314. 

Bouant,  325. 

Boudet,  329. 

Boudouard,  450. 

Boudouin  test,  285. 

Boyce,  210,  334,  335,  675. 

Boynton's  Device,  591. 

Boys,  424. 

Bragnier,  3. 

Brahmer,  441,  496. 

Bramkamp,  592. 

Brass,  432. 

Brauer,  355. 

Bread,  342,  356,  646. 

Bread,  hydrogenated  fats  in,  341. 

Bread  shortening,  342. 

Brebesol,  323. 

Brecht,  321. 

Bredig,  245,  279,  419. 

Bredig  method,  33. 

Bremen-Besigheimer,    7,   43,    105,    132, 

139,  185,  198,  323. 
Breteau,  137. 
Brief  for  Defendant,  649. 
Brief  for  Platintiff,  630. 
Brindley,  519. 
Brine,  temperature  of,  321. 
Brine,  use  of,  370. 

Briquettes  for  making  hydrogen,  502. 
Briquettes,  iron,  501. 
Briquettes  of  iron  oxide,  499. 
British  comptroller,  534. 
Brochet,  36,  85. 
Bromate,  potassium,  274. 
Bromide,  antimony,  164. 
Bromide  silver,  273. 
Bromide  test,  288. 
Bromides,  303. 
Bromides,  insoluble,  314. 
Brominated  fatty  acids,  392. 
Bromination,  heat  of,  101. 
Bromination  test,  303. 
Bromine,  113,  160,  164,  301,  443,  455. 
Bromine  compounds,  285. 


Bromine  reaction,  302. 

Bromine  test,  288. 

Brooks,  403,  405,  423,  425,  481. 

Brown,  85,  434. 

Brownell,  602. 

Browning,  property  of,  332. 

Brownlee,  480. 

Brudenne,  85.  • 

Brunjes,  207. 

Brunner,  484. 

Brunner,  Mond  &  Co.,  611. 

Bruno,  517. 

Bruno  Waser,  5. 

Bryant,  85. 

Bubbling  process,  25. 

Buchanan,  458. 

Bucknam,  584. 

Buffa,  561. 

Buffing  compound,  411. 

Bujanadse,  424. 

Bulletin  of  Imperial  Institute,  108. 

Bull's  acid,  314. 

Bulteel,  20. 

Bunte,  476. 

Burchenal,  159,  344,  345,  631,  636,  648, 

650,  651,  662,  671,  677,  679. 
Burchenal  interference,  684,  685. 
Burchenal  product,  696. 
Burdett  system,  562. 
Bureau  of  Animal  Industry,  326. 
Bureau  of  Animal  Industry  method,  308. 
Bureau  of  Mines,  601. 
Burnt  clay,  69. 
Burroughs,  418. 
Butter,  660. 
Butter,  artificial,  329. 
Butter  color,  332. 
Butter  fat  hydrogenated,  337. 
Butter,  hydrogenated  oil  in,  297. 
Butter-like  product,  648,  696. 
Butter-like  substance,  640. 
Butter,    property    of    browning    when 

heated,  332. 
Butter,  renovated,  329. 
Butter  substitute,  107,  346,  354,  684. 
Butter,  test  for  hardened  oil  in,  297. 
Buttlar,  32. 
Butyrates,  48. 
Butyric  acid,  337,  280. 
Butyrin,  337. 


INDEX 


717 


Butyrodiolein,  337. 

Butyro-palmito  olein,  337. 

Butyl  oleate,  90. 

By-product  fats,  348. 

By-product  hydrogen,  440. 

By-product   hydrogen,    purification   of, 

600. 

Byrne,  603. 
Byrom,  177. 

Cabaret,  86. 

Cacao  butter,  310. 

Cadmium,  246,  265. 

Caking  of  iron,  491. 

Calamary  oil,  392. 

Calcination,  nickel  oxide  obtained  by, 

115. 

Calcium,  150. 
Calcium  aluminate,  152. 
Calcium  borate,  191. 
Calcium-boron  fluoride,  156. 
Calcium  carbide,  467,  597. 
Calcium  carbonate  and  palladium,  316. 
Calcium  formate,  446. 
Calcium  hydride,  520,  533,  595. 
Calcium  manganite,  21. 
Calcium  nitrate,  155,  190,  452. 
Calcium  oxide,  152. 
Calcium  phosphate,  190. 
Calcium  silicofluoride,  156. 
Calcium  sulphate,  151. 
Calcium  vanadate,  155. 
California  commission,  602. 
California  petroleum,  418. 
Calvert,  69,  70,  71,  72. 
Calvert's  high  pressure  apparatus,  69. 
Calvert  system,  44. 
Cambace'res,  85. 
Camphene,  245. 
Camphor,  128. 

Canadian  Department  of  Mines,  241. 
Canadian  nickel  copper  matte,  236. 
Cancellit,  363. 
Candelite,  283,  284,  287,  311,  361,  362, 

363,  368,  373,  375,  386,  394. 
Candelite  in  toilet  soaps,  365. 
Candies,  335. 
Candles,  83,  381,  40d 
Candle  fish  oil,  411. 
Candle  industry,  373,  398. 


Candle  material,  fatty  acids  for,  378. 

Candles,  nickel  in,  381. 

Candle,  stearine,  378. 

Candolit,  363. 

Capacity  of  hardened  fats  for  holding 
water,  355. 

Caproic  acid,  337. 

Caproin,  337. 

Capryl  bodies,  332. 

Carbide,  calcium,  467,  597. 

Carbide,  iron,  502. 

Carbide,  nickel,  120,  138,  186,  222. 

Carbides,  220. 

Carbohydrates,  121,  411. 

Carbohydrates  and  hydrogenated  oil, 
343. 

Carbon,  149,  151,  173,  259,  438. 

Carbon,  active,  21. 

Carbon,  amorphous,  274. 

Carbon  as  catalyzer,  438. 

Carbon  bisulphide,  15, 160, 165, 166,  443, 
597,  598. 

Carbon  black  and  hydrogen  by  decom- 
position of  hydrocarbons,  481. 

Carbon  catalyzer,  150. 

Carbon  charged  with  hydrogen,  272. 

Carbon,  cocoanut,  273. 

Carbon,  colloidal,  420. 

Carbon  compounds,  treatment  with 
hydrogen,  173. 

Carbon,  crystalline,  274. 

Carbon  deposits,  removal  of,  436. 

Carbon  dioxide,  137,  169,  194,  231,  274, 
316,  443,  448. 

Carbon  dioxide  and  iron,  517. 

Carbon  dioxide,  boiling  point,  461. 

Carbon  dioxide,  removal  of,  465, 468, 599. 

Carbon  disulphide.  318. 

Carbon,  effect  on  fats,  186. 

Carbon,  formation  in  hydrogen  genera- 
tor, 492. 

Carbon,  in  making  hydrogen,  527. 

Carbon  monoxide,  20,  42,  110,  112,  166, 
169,  194,  210,  231,  233,  237,  240,  241, 
250,  274,  423,  437,  442,  443,  470,  595. 

Carbon  monoxide,  action  on  nickel,  229 

Carbon  monoxide  and  calcium  hydrate, 
reaction  between,  469. 

Carbon  monoxide  and  hydrogen  on  iron 
oxides,  action  of,  502. 


718 


INDEX 


Carbon  monoxide  and  steam  over 
catalytic  material,  451. 

Carbon  monoxide  and  water  vapor,  107. 

Carbon  monoxide,  boiling  point,  461. 

Carbon  monoxide,  conversion  into 
methane,  454. 

Carbon  monoxide,  dry,  217. 

Carbon  monoxide  equilibrium,  450. 

Carbon  monoxide,  generation  of,  521. 

Carbon  monoxide  in  hydrogen,  492. 

Carbon  monoxide  in  hydrogen,  presence 
of,  40. 

Carbon  monoxide  lime  and  steam,  444 

Carbon  monoxide,  liquefaction,  460. 

Carbon  monoxide,  removal  of,  467,  468, 
476,  480,  597,  599,  600. 

Carbon  monoxide,  removal  by  solvents, 
460. 

Carbon  monoxide,  removal  from  hydro- 
gen, 596. 

Carbon  monoxide,  replacement  by  hy- 
drogen, 444. 

Carbon  monoxide,  steam  and  alkali, 
hydrogen  from,  458. 

Carbon,  nascent,  150. 

Carbon,  oxides  of,  153,  611. 

Carbon  oxychloride,  230. 

Carbon,  tetrachloride,  67. 

Carbonate,  copper,  56. 

Carbonate,  nickel,  41,  52,  54,  56,  58,  120, 
128,  138,  142,  147,  154,  159,  185, 
177,  186,  187,  190,  193,  197,  200,  202, 
219,  224,  225,  233,  316,  437,  613,  617. 

Carbonate  of  nickel,  basic,  98. 

Carbonate,  regeneration  of,  446. 

Carbonates,  153. 

Carbonic  acid,  251,  448. 

Carbonic  oxide,  230,  232,  234,  237. 

Carbonic  oxide  gas,  521. 

Carbonium,  595. 

Carbonium  Co.,  472. 

Carbonizing  of  catalyzers,  113. 

Carbonyl  apparatus,  234. 

Carbonyl,  nickel,  20,  41,  43,  63, 119, 135, 
141,  177,  198,  204,  207,  210,  229,  232, 
233,  239,  443,  456,  480. 

Carbonyl,  poisonous  vapor,  233. 

Carbonyl  reaction,  204,  214,  217,  227. 

Carbonyl,  reviving  sluggish  nickel,  232. 

Carbonyl  test,  184. 


Carborundum,  173,  411. 

Carboxyl  group,  325. 

Caro,  40,  443,  462,  501. 

Carpenter,  597. 

Carrier  of  copper,  243. 

Carriers,  117,  151. 

Carriers,  effect  of  various,  248. 

Carriers  for  catalytic  metal,  178. 

Carriers,  hydrogen,  275. 

Carughi,  6. 

Carulla,  515. 

Casein,  332. 

Cast  iron,  267. 

Castor  oil,  29,  39,  88,  188,  242,  244,  248r 
250,  259,  275,  283,  297,  309,  313,  337, 
348,  359,  375,  381,  389,  394,  398,  409, 
659. 

Castor  oil,  hydrogenated,  284. 

Catalysis,  capriciousness  of,  619. 

Catalysis  effect  of  hydrides,  275. 

Catalysis,  nickel,  270. 

Catalyst  from  lixiviated  alkali  ferrite, 
459. 

Catalyst,  metal,  356. 

Catalyst,  osmium,  259. 

Catalysts,  production  at  low  tempera- 
ture, 146. 

Catalytic  action  of  nickel  oxides,  211. 

Catalytic  action,  use  of  formic  acid,  194. 

Catalytic  activity,  121. 

Catalytic  activity  of  iron  and  nickel, 
137. 

Catalytic  agent,  344. 

Catalytic  decomposition  of  carbon  mon- 
oide  with  nickel,  453. 

Catalytic  dehydrogenation  by  palla- 
dium, 257. 

Catalytic  efficiency,  development  of,  132. 

Catalytic  material,  exposure  to  a  partial 
vacuum,  158. 

Catalytic  material,  life  of,  113. 

Catalytic  material  prepared  from  nickel 
salts,  140. 

Catalytic  metal  in  oil,  319. 

Catalytic  nickel,  nickel  carbonyl  as  a 
source  of,  229. 

Catalytic  nickel,  peculiarities  of,  114. 

Catalytic  palladium,  cost  of,  63. 

Catalytic  palladium,  powerful,  315. 

Catalytic  plates,  432. 


INDEX 


719 


Catalytic     process,      development     by 

Kayser,  212. 

Catalytically  active,  nickel  black,  210. 
Catalyzer,  activation  by  oxygen,  260 
Catalyzer,  analysis  of  used,  227. 
Catalyzer,  amount  of,  99. 
Catalyzer  arc  process,  142. 
Catalyzer  balls,  160 

Catalyzer,  benzol  insoluble  bodies,  227. 
Catalyzer,  by  electric  arc,  142. 
Catalyzer  by  electrolysis,  175. 
Catalyzer,  carbon,  150,  259,  438. 
Catalyzer,  carbon  in,  133,  149. 
Catalyzer,  cerium  oxide,  21. 
Catalyzer,  cobalt  copper,  146. 
Catalyzer,  cobalt  oxide,  199. 
Catalyzer,  colloidal  sealed  in  oil,  160. 
Catalyzer,  coloration  by,  213. 
Catalyzer,  comparison  of  activity,  187. 
Catalyzer,  composite,  147. 
Catalyzer  containing  cobalt,  preparation 

of,  452. 
Catalyzer,  continuous  process  of  making, 

144. 

Catalyzer  cubes,  160. 
Catalyzer,  dehydrogenating,  270. 
Catalyzer,  detoxi cation,  162. 
Catalyzer  diaphragm,  639. 
Catalyzer,  effect  of  a  carrier,  187. 
Catalyzer,  effect  of  air,  110. 
Catalyzer,  effect  of  alumina,  168. 
Catalyzer,  effect  of  fine  division,  168. 
Catalyzer,  effect  of  fluorides,  156. 
Catalyzer,  effect  of  liquid  on,  13. 
Catalyzer,  effect  of  oxygen  on,  264. 
Catalyzer,  effect  of  phosphates,  190. 
Catalyzer,  effect  of  water,  221,  226. 
Catalyzer,  electrical  comminution,  217. 
Catalyzer,  electrical  conductivity,  182. 
Catalyzer,  electrical  disintegration,  142. 
Catalyzer,  electrically  disintegrated,  174. 
Catalyzer,  electrolytic,  257. 
Catalyzer,  extraction  of  fat,  214. 
Catalyzer,  filtration  of,  189. 
Catalyzer,  finely  divided,  624. 
Catalyzer,  finely  divided  nickel,  212. 
Catalyzer,  fineness  of,  624. 
Catalyzer,  flaky  nickel,  140. 
Catalyzer,  flaky,  recovery  of,  141. 
Catalyzer,  flocculated,  215. 


Catalyzer,  fluffy,  263. 
Catalyzer  for  cracking  oil,  420. 
Catalyzer  for  cracking  petroleum  oilsr 

426. 

Catalyzer  for  fatty  acids,  263. 
Catalyzer  for  hydrocarbons,  151. 
Catalyzer  for   making    hydrogen,  451,. 

457,  476,  480. 
Catalyzer  for   oxidation   of    ammonia, 

256. 

Catalyzer  for  propylene,  260. 
Catalyzer,  formates,  191. 
Catalyzer,  formates  for,  190. 
Catalyzer,  free  nickel  necessary,  211. 
Catalyzer  from  nickel   carbonate,   159,. 

187. 

Catalyzer  from  nickel  hydrate,  172. 
Catalyzer  gauze,  electrically  heated,  449. 
Catalyzer,  ignition,  167,  264. 
Catalyzer,  impurities  in  oil,  311. 
Catalyzer,  in  Bergius  process,  529. 
Catalyzer,  inclined  reducing  tube,  157. 
Catalyzer  in  oil,  43. 
Catalyzer,  iron-copper,  146. 
Catalyzer,  iron  oxide,  199. 
Catalyzer,  Kast,  129. 
Catalyzer,  Kayser  Kieselguhr,  131. 
Catalyzer,  Lane  process,  171. 
Catalyzer,  lead  oxide,  21. 
Catalyzer,  magnetic,  169,  227. 
Catalyzer,  making,  610. 
Catalyzer,  manganese  oxide,  21. 
Catalyzer,  metallic  condition  of,  130. 
Catalyzer,   metallo-organic  compounds, 

188. 

Catalyzer,  metallo-organic  salts,  130. 
Catalyzer,  methods  of  preparation,  165. 
Catalyzer,  nickel,  98,  118,  284,  324,  325, 

357,  361. 

Catalyzer,  nickel  alumina,  171,  176,  192. 
Catalyzer,  nickel  and  carbon,  186. 
Catalyzer,  nickel  and  glass,  176. 
Catalyzer,  nickel  and  nickel  carbonate, 

225. 

Catalyzer,  nickel  borate,  179. 
Catalyzer,  nickel  borate  and  silicate,  185. 
Catalyzer,  nickel  carbonate,  190,  225. 
Catalyzer,  nickel  carbonyl,  177,  207,  229, 

456. 
Catalyzer,  nickel-charcoal,  149. 


720 


INDEX 


Catalyzer,  nickel-cobalt,  128. 
Catalyzer,  nickel-copper,  128,  147,  186. 
Catalyzer,  nickel  flake,  219. 
Catalyzer,  nickel  formate,  225. 
Catalyzer,  nickel  from  carbonyl,  237. 
Catalyzer,  nickel-fullers'  earth,  171. 
Catalyzer,  nickel  kieselguhr,  206,  241. 
Catalyzer,  nickel-magnesia,  456. 
Catalyzer,  nickel  oleate,  195,  197,  198. 
Catalyzer,  nickel  on  pumice,  50. 
Catalyzer,  nickel  oxide,  271,  596. 
Catalyzer,  nickel-palladium,  147. 
Catalyzer,  nickel-platinum,  147. 
Catalyzer,  nickel  salt,  340. 
Catalyzer,  nickel  sheet  and  wire,  167. 
Catalyzer,  nickel-silica,  177,  192. 
Catalyzer,  nickel-silver,  147. 
Catalyzer,  nickel  soap,  195. 
Catalyzer,  non-pyrophoric,  159, 169, 171, 

276,  316. 

Catalyzer,  non-soap  forming,  263. 
Catalyzer,  oleates  and  stearates,  195. 
Catalyzer  on  fibrous  material,  56. 
Catalyzer,  organic  salts  of  nickel,  cobalt, 

iron  and  copper,  193. 
Catalyzer,  oxide  of  iron,  21. 
Catalyzer,  palladium,  62,  100,  242. 
Catalyzer,  palladium,  cost  of,  256. 
Catalyzer,  palladium  on  coke,  259. 
•Catalyzer,  percentage  of,  99,  102. 
Catalyzer,  period  of  activity,  113. 
Catalyzer,  platinum,  283. 
Catalyzer,  platinum  and  carbon,  259. 
•Catalyzer,  platinum  black,  246. 
Catalyzer,  platinum  hydroxide,  249. 
Catalyzer,  platinum  on  charcoal,  259. 
Catalyzer,  porous,  624. 
Catalyzer  poison,  14,  109,  112,  113,  118, 

153,  155,  160,  164,  166,  189,  198,  208, 

223,  243,  247,  250,  254,  255,  264,  270, 

419,  420,  442,  443,  453,  454,  485,  532, 

610,  615,  618,  620. 
•Catalyzer  poison,  liquids  as,  613. 
Catalyzer  poisons,  removing  from  oil, 

161. 

•Catalyzer  poisons,  resistance  to,  181. 
Catalyzer,  porous  metal  plates,  60. 
Catalyzer  prepared  from  charcoal,  150. 
Catalyzer,  preparation  of,  135,  413. 
Catalyzer,  preserved  in  oil,  159,  160. 


Catalyzer  promoters,  154,  168,  223,  455. 

Catalyzer,  pyrophoric,  186. 

Catalyzer,  recovered,  215. 

Catalyzer,  recovering,  43. 

Catalyzer,  recovery  of,  62,  132,  170, 171, 
188/241,  428. 

Catalyzer,  reduced  nickel  oxide,  201. 

Catalyzer  reducer,  413. 

Catalyzer,  reducing  chamber,  145. 

Catalyzer-reducing  device,  413. 

Catalyzer  reduction,  explosion  dangers, 
169. 

Catalyzer,  reduction  in  ammonia,  171. 

Catalyzer,  reduction  in  hydrocarbons, 
198. 

Catalyzer,  reduction  in  naphthol,  ace- 
tanilid,  anthracene,  220. 

Catalyzer,  reduction  in  oil,  187. 

Catalyzer,  reduction  in  paraffin,  222. 

Catalyzer,  reduction  in  vacuum,  139. 

Catalyzer,  reduction  in  various  sus- 
pensory bodies,  222. 

Catalyzer,  reduction  in  wax,  148,  198. 

Catalyzer,  reduction  of,  134,  139,  156, 
611. 

Catalyzer,  reduction  process  for,  171. 

Catalyzer,  reduction  under  pressure, 
169. 

Catalyzer,  regeneration  of,  116. 

Catalyzer,  removal  of  hydrides,  137. 

Catalyzer,  rendering  non-pyrophoric, 
276. 

Catalyzer,  reoxidation  of,  142. 

Catalyzer,  reuse  of,  218. 

Catalyzer,  revivification  of,  105. 

Catalyzer,  sealed  in  wax,  186. 

Catalyzer,  semi-reduced,  209. 

Catalyzer,  shipment  of,  160. 

Catalyzer,  silicates  in,  169. 

Catalyzer  smell,  186. 

Catalyzer,  specific  gravity  of,  151. 

Catalyzer,  stationary,  22. 

Catalyzer,  stearic  soap,  129. 

Catalyzer,  sulphates  in,  163. 

Catalyzer,  tablets,  160. 

Catalyzer,  Tamari's,  151. 

Catalyzer,  tests  of,  214. 

Catalyzer,  too  high  reduction  tempera- 
ture, 627. 

Catalyzer,  traces  in  fat,  411. 


INDEX 


721 


Catalyzer,    treatment    with    hydrogen, 

171. 

Catalyzer,  treatment  with  nitrogen,  159. 
Catalyzer,  trinitrophenol  salts,  129. 
Catalyzer,  use  of  a  carrier,  479. 
Catalyzer,  use  of  metal  soaps,  40. 
Catalyzer,  use  of  sugar  in  making,  175. 
•Catalyzer,  use  of  wool  in,  171,  262. 
Catalyzer,  used,  analysis  of,  219. 
Catalyzer,  voluminous,  121, 199. 
Catalyzer,  washing  precipitate,  627. 
Catalyzer,  Wesson,  172. 
Catalyzer,  Wilbuschewitsch,  133. 
Catalyzer,  wire  for,  427. 
Catalyzer,  wire  gauze,  449. 
Catalyzers  and  their  role  in  hydrogena- 

tion  processes,  108. 
Catalyzers,  carbonizing  of,  113. 
Catalyzers,  classification  of,  117. 
Catalyzers,  containing  silica,  173. 
Catalyzers,  effect  of  hydrides,  275. 
Catalyzers  for  making  hydrogen,  455. 
Catalyzers,  ignition,  251. 
Catalyzers,  in  making  hydrogen,  513. 
Catalyzers,  loss  of  efficiency,  113. 
Catalyzers,  metal  soaps  for,  129. 
Catalyzers  of  high  activity,  135. 
Catalyzers  of  the  nickel  and  cobalt  type, 

24. 

Catalyzers,  resistance  to  poisons,  596. 
Catalyzers,  salts  of  platinum,  249. 
Catalyzers,    temperature   of   reduction, 

109,  112. 

Catalyzers,  various  oxides,  402. 
Catalyzers,  water  in,  216. 
Cathode  atomization,  74. 
Cathode,  metal,  275. 
Cathode,  nickel  gauze,  280. 
Causes  of  explosion,  592. 
Caustic  potash  electrolyte,  559. 
Caustic  soda,  440. 
Caustic  soda  and  aluminum,  595. 
Caustic  soda  and  ferrosilicon,  595. 
Caustic  soda  electrolyte,  547,  552,  559, 

561,  571. 
Cement,  254. 

Centrifugal  gas  separator,  467. 
Cerates,  410. 
Cereal  baking  products,  hardened  oil  in, 

343. 


Cerium,  150, 151,  254,  259,  264,  279. 

Cerium  ammonium  nitrate,  153. 

Cerium  nitrate,  153,  456. 

Cerium  oxide,  119,  402. 

Cerium  oxide  catalyzer,  21. 

Ceylon  cocoanut  oil,  367,  375. 

Chabasite,  261. 

Chaillaux,  534. 

Challenger,  423. 

Chapman,  313. 

Chappell,  434. 

Charcoal,  109,  136,  175,  187,  190,  259. 

Charcoal,  absorption  of  gases  by,  532. 

Charcoal  alumina,  150. 

Charcoal,  animal,  186,  249,  259. 

Charcoal  catalyzer,  150. 

Charcoal,  cocoanut,  274. 

Charcoal-lime,  150. 

Charcoal-nickel,  136. 

Charcoal-nickel,  activated,  150. 

Charcoal-nickel  catalyzer,  149. 

Charcoal-palladium  catalyzer,  309. 

Charcoal,  retention  of  oxygen  by,  274. 

Charcoal,  wood,  274. 

Charitschkoff,  419. 

Charlton,  62. 

Charts,  triangular,  644. 

Cheese,  addition  of,  357. 

Cheesy  odor,  363. 

Chemical  considerations,  41. 

Chemical    properties  of    hardened    oil, 

347. 

Chemically-active  rays,  35,  36,  41. 
Chemiker-Zeitung,  120. 
Chemischen  Fabrik  Greisheim-Elektron, 

444,  445,  525. 

Chem.  Fabr.  auf.  Actien,  128. 
Chem.  Fab.  vorm.  Goldenberg,  252. 
Cherry,  435. 
Chichibabin,  421. 
Chill  roll,  320. 
Chill  roll,  use  of,  336. 
Chinese  wood  oil,  361,  396,  400,  411. 
Chisholm,  57. 
Chlorate,  barium,  273. 
Chlorate,  copper,  273. 
Chlorate,  lead,  273. 
Chlorate,  mercury,  273. 
Chlorate,  potassium,  273. 
Chlorate,  sodium,  273. 


722 


INDEX 


Chloric  acid,  273. 

Chloride,  barium,  250,  257. 

Chloride,  cupric,  230. 

Chloride,  cuprous,  231. 

Chloride,  ferric,  273. 

Chloride,  mercuric,  247. 

Chloride,  mercury,  144. 

Chloride,  nickel,  131,  166,  328. 

Chloride  of  zinc  process,  3. 

Chloride,  palladium,  55,  63,  78,  100,  140, 

242,  246,  256,  270. 
Chloride,  palladious,  253,  255. 
Chloride,  platinum,  147,  242,  260,  264. 
Chloride,  silver,  273. 
Chloride,  sodium,  164,  166. 
Chloride,  sulphur,  164. 
Chloride,  tin,  164. 
Chloride,  zinc,  164. 
Chlorides,  162. 
Chlorides  of  platinum   and  palladium, 

249. 

Chlorides  of  the  platinum  metals,  243. 
Chlorine,  109,  112,  113,  118,  153,  160, 

166,  198,  208,  440,  443,  451,  453,  455, 

596,  610,  615. 
Chlorine    as    a    substitute    for    iodine, 

2. 

Chlorine  determination,  316. 
Chloroform,  15,  67,  443. 
Chlorohydroxy,  fatty  acids,  84. 
Chloroplatinate,  potassium,  243. 
Chlorplatinic  acid,  248. 
Chlorplatinic  acid,  reduction  of,  247. 
Chlor-stearic  acid,  2. 
Chocolate,  335. 
Chocolate  creams,  346. 
Cholesterol,  283,  284,  289,  291,  294,  310, 

311. 

Chromate,  barium,  155. 
Chromates,  178. 
Chromium,  151,  276,  422,  426,  428,  455, 

499. 

Chromium  hydrate,  262. 
Chromium  nitrate,  155,  453,  455. 
Chromium  oxide,  152,  501. 
Chrysalis  oil,  311,  361,  402. 
Chrysalis  oil  refining,  311. 
Churchill  &  Co.,  589. 
Cinnamic  acid,  86,  187,  222,  260. 
Cinnamic  acid,  methyl  ester,  86. 


Cinnamic  acid,  sodium  salt,  86. 

Cinnamylcocaine,  210. 

Circulation  of  hydrogen,  26. 

Citraconic  acid,  280. 

Citrates,  48. 

Citrates  in  electrolyte,  562. 

Clark,  481. 

Classen,  257. 

Classification  of  catalyzers,  117. 

Claude,  466. 

Claude  apparatus,  468. 

Claude  Co.,  467. 

Clausmann,  502. 

Claver,  501. 

Clay,  133,  154,  168,  173,  187,  192,  197, 
252,  254,  423,  429,  433,  501. 

Clay,  porous,  131. 

Clay,  porous  burnt,  69. 

Clayton,  355. 

Cleavage,  379,  394,  398. 

Cleavage  reagent,  29. 

Clupanodonic  acid,  88,  287,  360,  390r 
392,  440. 

Clupanodonin,  396. 

Coal  gas,  240. 

Coal,  method  of  hydrogenating,  431. 

Coal,  treatment  of,  437. 

Coal  used  as  a  carrier,  254. 

Coast,  436. 

Cobalt,  24,  54,  69,  95,  96,  110,  112,  136,, 
151,  152,  158,  175,  187,  190,  198,  230, 
235,  248,  270,  275,  276,  404,  422,  423, 
426,  427,  428,  430,  433,  438,  451,  455, 
502,  531,  605,  609,  611,  613,  618,  621, 
628. 

Cobalt  anode,  577. 

Cobalt  catalyzer,  452. 

Cobalt  chloride,  149. 

Cobalt-copper,  136. 

Cobalt,  fatty  acid  salts,  193. 

Cobalt,  flaky,  141. 

Cobalt  formate,  191. 

Cobalt  gauze,  449. 

Cobalt  hydrate,  146. 

Cobalt  hydride,  275. 

Cobalt  hydroxide,  88. 

Cobalt  in  making  hydrogen,  448. 

Cobalt-nickel  catalyzer,  128. 

Cobalt  nitrate,  146,  452. 

Cobalt,  organic  salts  of,  47,  130. 


INDEX 


723 


Cobalt  oxide,  88,  112,  146, 199,  262,  402, 

452. 

Cobalt,  reduced,  267. 
Cobalt  soap,  195. 
Cobalt-steel,  136. 
Cobalt  solutions,  reduction  of,  170. 
Cocoa  butter,  335. 
Cocoa  butter  substitutes,  337. 
Cocoanut  carbon,  273. 
Cocoanut  charcoal,  gas-free,  274. 
Cocoanut  oil,  88,  282,  290,  309,  319,  331, 

333,  335,  355,  359,  364,  365,  366,  368, 

369,  370,  373,  375,  388,  393,  398,  409, 

439,  692. 

Cocoanut  oil  soap,  recipe  for,  368. 
Cocoanut  oil  soaps,  367. 
Cocatalysts,  262. 

Codex  alimentarius  Austriacus,  294. 
Cod  liver  oil,  242,  275,  310,  348,  637. 
Cod  oil,  162,  301. 
Coefficient  of  reduction,  126. 
Coefficients  of  digestibility,  692. 
Co-extended  metal,  136. 
Coke,  75,  259,  423. 
Coke  and  palladium  catalyzer,  62. 
Coke,  hydrogen  from,  447. 
Coke  oven  gas,  442. 
Cold  process  shaving  soap,  368. 
Cold  process  soaps,  369. 
Cold  process  soape,  talgol  in,  366. 
Coleman,  241. 
Colletas,  63,  256. 
Collins,  550. 

Colloid,  nitrogenous,  171. 
Colloid  protective,  244,  255,  257. 
Collodial  carbon,  420. 
Colloidal  catalyzer,  disadvantage  of,  309. 
Collodial  catalyzer,  sealed  in  oil,  160. 
Collodial    hydroxides    of   osmium    and 

ruthenium,  258. 
Colloidal  nickel,  122,  189,  194,  207,  217, 

417,  437. 

Colloidal  nickel  catalyzers,  160,  198. 
Colloidal  nickel  oxide,  218,  222. 
Colloidal  nickel  suboxide,  120. 
Colloidal  osmium,  261. 
Colloidal  palladious  oleate,  253. 
Colloidal  palladium,  242,  250,  255,  270, 

390,  404,  659. 
Colloidal  palladium  catalyzer,  306. 


Colloidal  palladium  hydroxide  solution, 

253. 

Colloidal  platinum,  33,  245,  259,  600. 
Colloidal  rare  metals,  600. 
Colloidal  solutions,  208. 
Colloidal  suboxides,  209. 
Colloidal  suspensions  of  the  metals,  247. 
Colloids  of  platinum  group,  252. 
Colophony,  297,  403. 
Color  of  fatty  acids,  378,  380. 
Color  of  gasolene,  422. 
Color  of  product,  319. 
Color  of  product,  improvement  of,  331. 
Color  of  soaps,  381. 
Color  reactions,  293. 
Color  stability,  336. 
Color  stabilizer,  336. 
Color  test  for  oils,  301. 
Color  test,  Tortelli  &  Jaffe,  301. 
Color  tests  of  oil,  effect  of  hydrogenation 

on,  285,  295. 

Coloration  by  catalyzer,  213. 
Colorimetric  comparison  with  a  nickel 

solution,  327. 
Colori metrical  determination  of  nickel, 

296. 

Colza/oil,  see  Rape  Oil. 
Commercial  development  of  Wilde  proc- 
ess, 2. 

Commercial  side  of  fat  hardening,  361. 
Comminuted  hardened  oil,  646. 
Comminuted  hardened  oil  with  wheat 

flour,  340. 

Comminution,  electrical,  174. 
Comparison  of  conditions  before  war,, 

352. 

Composite  catalyzers,  147. 
Compound,  change  in  color  on  standing; 

335. 

Compound  cooler,  322. 
Compound  lard,  96,  701. 
Compressed  Gas  Mf'rs  Ass'n,  603. 
Compression  of  acetylene,  473. 
Compressor  for  hydrogen,  593. 
Condensation  products,  232. 
Condensation  products  from  unsaturated 

hydrocarbons,  421. 
Condensers,  telephone,  409. 
Conditions  before  war,  comparison  of, 

352. 


724 


INDEX 


Conductivity  apparatus,  216. 
Conductivity,  electrical,  124,  182,  200, 

210,  211,  216. 

Conductivity  of  nickel  oxide,  208. 
Conductivity    of   reduced    nickel    com- 
pounds, 202. 
Conductivity  of  reduced  nickel  oxide, 

201. 

Confectionery,  346. 
Confectionery    compounds,    containing 

hydrogenated  oil,  335. 
Connstein,  29,  256. 
Conroy,  108. 
Conservatoire     National     des     Art    et 

Metier,  567. 
Consortium  fur  Elektro-chem.  Ind.  ges. 

m.  b.  H.,  523. 
Constant  circulation  and  contact  of  the 

hydrogen  gas,  25. 
Constants  in  the  electrolysis  of  water, 

536. 

Constants  of  hydrogenated  oil,  281. 
Contact  material  for  making  hydrogen, 

502. 
Content  of  free-fatty  acid,  increase  of, 

140. 

Content  of  nickel  in  foodstuffs,  327. 
Continental     Caoutchouc     and     Gutta 

Percha  Co.,  425. 
Continuous  methods,  643. 
Continuous  process  of  making  catalyzer, 

144. 

Control,  Burdett  automatic,  563. 
Control  of  electrolyzers,  automatic,  585. 
Conversion  of  hydrocarbons  and  steam 

into  hydrogen,  479. 
Conversion  of  mineral  oils  into  oils  of 

lower  specific  gravity,  21. 
Conversion  of  oleic  acid  into  palmitic 

and  acetic  acids,  3. 
Converter,  415. 
Converting  oleic  acid  into  stearic  acid, 

problem  of,  1. 
Cooking  fats,  338,  357. 
Cooking  oils,  354. 
Cooking,  shortening  for,  345. 
Copal,  96. 
Copper,  39,  54,  96,  109,  112,  152,  161, 

168,  173,  190,  194,  198,  208,  230,  236, 
i     246,  260,  265,  270,  271,  275,  294,  379, 


404,  422,  423,  427,  429,  430,  432,  437, 
502,  504,  513,  529,  605,  609,  611,  614, 
618,  621,  628. 

Copper  and  nickel  catalyzer,  56. 

Copper  and  nickel  hydrates,  55. 

Copper  as  a  carrier,  243. 

Copper,  atomic,  148. 

Copper,  basic  oleate,  196. 

Copper  carbonate,  56,  194. 

Copper  catalyst  activators,  195. 

Copper  catalyzer,  52. 

Copper  chlorate,  273. 

Copper  chloride,  149,  467. 

Copper  chloride  purifying  agent,  599, 
600. 

Copper-coated  nickel,  167. 

Copper,  fatty  acid  salts,  194. 

Copper  formate,  191,  194. 

Copper,  gases  in,  278. 

Copper  hydrate,  146,  162,  186,  264. 

Copper  hydrate  treatment  of  oils,  162. 

Copper  hydride,  196. 

Copper-iron  couple,  459. 

Copper-nickel  catalyzer,  128. 

Copper  nitrate,  55,  56,  146,  169,  194, 
434,  456. 

Copper  nitrate,  temperature  of  decom- 
position, 170. 

Copper  on  asbestos,  84. 

Copper,  organic  salts  of,  47. 

Copper  oxalate,  194. 

Copper  oxide,  116,  130,  135,  146,  168, 
402,  425,  448,  455,  501. 

Copper  platinochloride,  243. 

Copper-platinum,  260. 

Copper,  reduced,  267. 

Copper  soap,  129,  195. 

Copper  sulphate,  273. 

Copper  sulphide,  434. 

Copper  wire,  57,  267. 

Copra  oil,  354. 

Copra  oil,  replacement  of,  361. 

Cordes,  409. 

Corn  husks,  208. 

Corn  oil,  87,  96,  282,  334,  335,  343,  396, 
408,  410,  439. 

Corn  oil  as  substitute  for  olive  oil,  410. 

Corn  oil,  expansion  of,  411. 

Corn  oil,  substitute  for  lard,  350. 

Corn  oil,  substitute  for  olive,  350. 


INDEX 


725 


Corona,  418. 
Correlli,  138,  204. 
Coryphol,  287,  363,  399. 
Cost  of  catalytic  palladium,  63. 
Cost  of  electrolytic  plant,  538. 

Cost  of  fish  oils,  353. 

Cost  of  hardening,  352. 

Cost  of  oleo-stearine,  319. 

Cotton  oil,  20,  39,  48,  52,  55,  56,  58, 
89,  96,  98,  104,  123,  128,  130,  134,  137, 
138,  140,  143,  148,  149,  155,  161,  164, 
175,  177,  179,  181,  185,  194,  200,  201, 
205,  213,  215,  216,  217,  223,  238,  242, 
248,  255,  263,  281,  282,  283,  285,  289, 
290,  291,  301,  304,  305,  306,  308,  319, 
323,  325,  328,  331,  334,  335,  338,  339, 
341,  343,  344,  345,  346,  347,  348,  349, 
352,  354,  357,  368,  383,  396,  399,  407, 
409,  410,  609,  610,  637,  639,  645,  655, 
660,  671,  675,  692,  697,  701,  703. 

Cotton  oil  as  shortening  material,  647. 

Cotton  oil,  composition  of,  694. 

Cotton  oil  fatty  acids,  298. 

Cotton  oil,  free  of  aldehydes,  218. 

Cotton  oil,  hardening  of,  225. 

Cotton  oil  in  margarine  industry,  361. 

Cotton  oil  purified  by  steam,  214. 

Cotton  oil,  self-thickened,  319. 

Cotton  stearine,  96. 

Cowper-Coles  Generator,  558. 

Cox,  407. 

Cracking  of  gas  oils  in  various  atmo- 
spheres, 435. 

Cracking  of  petroleum,  420. 

Cracking  oils,  150. 

Cracking  petroleum,  154. 

Cracking  process  of  Wells,  430. 

Cracking  tars  and  oils,  438. 

Cracking  Texas  solar  oil,  425. 

Cracking  under  pressure,  419. 

Craine,  157,  159. 

Cripps,  611,  620. 

Crisco,  16,  294,  350,  653,  690,  707. 

Crisco,  advantages  of,  635,  636. 

Crisco  and  Kream-Krisp,  G30. 

Crisco,  sales  of,  635. 

Criticism  of  hardened  oil,  371. 

Croconic  acid,  salts  of,  231. 

Crocus,  411. 

Crocus  martis,  452. 


Crosfield,  7,  38,  131. 

Crosfield  &  Sons,  155,  134,  212,  406,  605, 

633,  661,  666,  671,  682. 
Cross,  437. 

Crossley,  155,  163,  240,  300,  534. 
Croton  oil,  297,  637,  658,  660,  661. 
Crotonic  acid,  280. 
Cruciferous  oil,  316. 
Crutolein,  368. 
Crutolin,  362,  374,  383. 
Crystalline  carbon,  274. 
Crystallization  of  stearine,  354. 
Cucumber  seed,  oil  from,  357. 
Cumarin  as  flavoring  material,  332. 
Cuprene,  611. 
Cupric  chloride,  230. 
Cuprous  chloride,  148,  231,  460,  467,  4C3, 

480. 
Cuprous  chloride  purifying  agent,  599, 

600. 

Cuprous  chloride  solution,  235. 
Curme  method  for  separation  of  gc?esf 

531. 

Curran,  517. 
Curve  showing  solubility  of  hydrogen  in 

metals,  266. 

Curves,  absorption,  308. 
Curves  of  hydrogenation,  101,  226. 
Custis,  62. 

Cyanide,  nickel  potassium,  124,  208. 
Cyanide,  potassium,  165,  273,  525. 
Cyanogen,  596. 

Cyclic  hydrogenation  process,  22. 
Cyclic  process  for  producing  hydrogen, 

530. 

Cyclobutane,  258. 
Cyclohexane,  160,  257. 
Cyclohexanol,  13,  86, 153. 
Cyclohexanone,  86. 
Cylinders,  finely-divided  iron  in,  592. 
Cylinders  for  hydrogen,  592. 
Cylinders,  hydrogen,  440,  533. 
Cylinders,  oil  in  gas,  592. 

D'Arsonval,  537. 
Dab  oil,  392. 
Dalla,  402. 
Damar,  96, 
Dampierre,  436. 
Danger  of  explosion,  169. 


726 


INDEX 


Dansette,  558. 

Danckwardt,  423. 

Dark  soaps,  372. 

Daughters,  357. 

David,  60. 

Davidsohn,  287,  302,  398. 

Davidson,  435,  438. 

Davis-Bourrionville  Co.,  electrolyzer, 

582. 

Davy  wire  gauze,  590. 
Day,  10,  20,  433. 

Day's  process  for  petroleum  oils,  10. 
de  Bassano,  85. 
Debus,  606. 

Decision  of  Judge  Hand,  700. 
Decision  of  Judge  Hand,  comments  on, 

707. 

Decomposition  of  carbonyl,  237. 
Decomposition  of  fats,  oils  and  waxes,  29. 
Decomposition  of  nickel  carbonyl,  236. 
De  'Conno,  84. 
Decrolin,  371. 
Degree  of  reduction,  determination  of, 

28. 

Deguide,  517. 
De  Hemptinne,  3,  30. 
De  Hemptinne's  process,  83. 
Dehydrogenating  catalyzers,  271. 
Dehydrogenation,  152,  257,  268. 
Dehydrogenation  of  oils,  256. 
Dehydrogenation  with  copper,  271. 
de  Jahn,  68. 
de  Kadt,  37,  40,  129. 
De  la  Fresnaye,  530. 
Dellwik-Fleischer  System,  486. 
Delmard,  541. 
de  Montlaur,  251,  256. 
Dempster  System,  507. 
De  Nordske  Fabrik,  353. 
De  Nordiske  Fabriker,  360. 
De  Nordiske  Fabriker  De-No-Fa  Aktie- 

selskap,  129. 
Deodorization,  26,  351. 
Deodorization,  steam-vacuum,  319. 
Deodorized  fish  oils,  360. 
Deodorized  low-grade  fats,  use  of,  328. 
Deodorizing  and  decolorizing  chrysalis 

oil,  402. 

Deodorizing  cocoanut  oil,  88. 
Deodorizing  oils,  88. 


Deodorizing  with  hydrogen,  87. 

De  Paoli,  79. 

Department  of  Commerce,  360. 

Deposited  nickel,  57. 

Deposition  of  carbon  in  making  hydro- 
gen, 510. 

Desulphurizing  petroleum,  11. 

Detection  of  traces  of  nickel,  294. 

Detection  of  nickel,  89. 

Detection  of  small  quantities  of  nickel, 
296. 

Determination  of  nickel  in  fats,  328. 

Detonation  of  nickel  carbonyl,  231. 

Detoxication,  162. 

Deveaux,  333. 

Devik,  36,  72. 

Dewar,  54,  56,  146,  233,  237,  270,  613. 

Dewar  &  Liebmann  process,  54. 

de  Wilde,  2,  247,  274,  608,  612. 

Dextrine,  122,  200,  257,  428,  452. 

Dialyzed  palladious  hydroxide,  247. 

Diaphragm,  asbestos,  537,  559,  560,  563, 
565,  570,  578,  581,  584,  589,  591. 

Diaphragm,  electrolyzer  without,  555. 

Diaphragm,  metallic,  561. 

Diaphragm,  woolen,  537. 

Dibdin,  21. 

Dicke,  509. 

Diedrichs,  309. 

Dieffenbach,  447,  449,  499. 

Diels,  310. 

Diffusion  of  gas,  443. 

Diffusion  process,  467,  531. 

Digestibility,  coefficients  of,  692. 

Digitonin  method,  283,  308,  310. 

Diglyceride,  348. 

Dihydrocholesterol,  283. 

Di-hydrophenanthrene,  267. 

Dihydrophorene,  270. 

Dihydroquinine,  210. 

Dimethylglyoxime,  294,  304,  305,  309, 
328. 

Dimethylglyoxime  test,  288. 

Dimethylglyoxime  test,  for  nickel,  295, 
296. 

Di  Nola,  294. 

Dioleopalmitin,  323. 

Dioleostearine,  323. 

Dioxide,  carbon,  231,  274. 

Dioxide,  hydrogen,  33. 


INDEX 


727 


Dioxide,  osmium,  249. 

Diphenylamine,  222. 

Diphenyl  diacetylene,  187. 

Disulphide,  carbon,  15. 

Discharge,  electrical,  74,  435. 

Disintegration,  electrical,  174. 

Distearopalmitin,  323. 

Distillation  of  fatty  acids,  380. 

Disulphide,  carbon,  443. 

Dobereiner,  251. 

Doering,  159. 

Dog,  feeding  experiments  with,  339. 

Dogfish  oil,  163,  411. 

Dohmen,  575. 

Dolomite  lime,  457. 

Doratol,  363. 

Dough,  viscosity  of,  342. 

Downing,  435. 

.Dreymann,  92. 

Drummond,  355. 

Dry  hydrogen,  127. 

Drying  agents,  140. 

Drying  oils,  380. 

Dubbs,  11. 

Dubovitz,  80,  291,  380,  398. 

Du  Motay,  444. 

Dural,  363. 

Durettol,  363. 

Durolit,  363. 

Durotal,  363. 

Durotol,  295,  399. 

Durotin,  363. 

Duru,  363. 

Durutol,  363. 

Earth,  infusorial,  58,  98. 

Earthenware,  porous,  531. 

Earthenware  tubes,  500. 

Earthenware,  unglazed,  450. 

Eastwick,  516. 

Edgar,  268. 

Edibility  of  hardened  oil,  347. 

Edibility  of  hydrogenated  oils,  323,  326. 

Edibility  of  whale  oil,  337. 

Edible  fats,  149,  649. 

Edible  fats,  first  information  on,  352. 

Edible  fats,  fish  oil  in,  302. 

Edible  fats  in  manufacture  of  margarine, 

331. 
Edible  fats,  pressing,  334. 


Edible  hydrogenated  fats,  630. 
Edible  hydrogenated  oils,  319,  338. 
Edible  oil  composition,  331. 
Edible  oil,  hardening  of,  71,  72. 
Edible    product    free    from    catalytic 

metal,  348. 
Edible  products  obtained  by  hydrogena- 

tion,  338. 
Edison,  141,  171. 

Effect  of  agitation,  26,  82,  99,  102. 
Effect  of  hydrogen  without  a  catalyzer, 

87. 

Effect  of  liquid  on  nickel  catalyzer,  13. 
Effectiveness  of  palladium  catalyzer,  242. 
Effect  of  pressure,  85,  97,  101. 
Effect  of  temperature,  92,  97,  101. 
Efrem,  252. 
Egg  yolk,  332. 
Egloff,  418. 
Egyptian  cottonseed  oil,  hydrogenation 

of,  137. 

Egyptian  cottonseed  oil,  use  of,  353. 
Elaeomargaric  acid,  401. 
Elaidic  acid,  297. 
Elaidin,  85. 
Eldred,  135,  448. 

Electric  arc  decomposition  of  water,  558. 
Electric  conductivity,  119. 
Electric  discharge,  44,  74. 
Electric  discharge  process,  4. 
Electric  discharge,  silent,  33. 
Electric  furnace,  271. 
Electric  resistance,  216. 
Electrical  comminution,  217. 
Electrical  comminution  of  nickel,  142, 

174. 
Electrical  conductivity,  124,   182,  208, 

210,  216. 
Electrical    conductivity,    determination 

of,  200. 

Electrical  conductivity,  lack  of,  211. 
Electrical  discharge,  435. 
Electrical  discharge,  effect  of,  30. 
Electrical  discharge,  silent,  73. 
Electrical  disintegration,  142. 
Electrical  disintegration  method,  246. 
Electrical  disintegration  of  metal,  174. 
Electrical  energy,  generation  of,  516. 
Electrical  process  of  De  Hemptinne,  83. 
Electrical  testing  laboratories,  568. 


728 


INDEX 


Electrical  treatment  of  oils,  61. 

Electrically-charged  particles  from  plati- 
num, 269. 

Electrically  heated  catalyzer  gauze,  449. 

Electrically  heated  purifier  of  Knowles, 
600. 

Electricity,  use  of,  3. 

Electrode,  bipolar,  588. 

Electrode,  cobalt,  577. 

Electrode,  corrugated,  572. 

Electrode,  nickel,  539,  560,  571,  572,  583. 

Electrode,  nickel  and  platinum,  280. 

Electrode,  platinum,  562. 

Electrode  of  wire,  581. 

Electrodes,  bipolar,  541. 

Electrodes,  lead,  544. 

Electrodes,  nickel,  5. 

Electrodes,  platinum,  5. 

Electrodes  preventing  gas  diffusion,  581. 

Electrolabs,  578. 

Electrolysis,  catalyzer  by,  175. 

Electrolysis  of  brine,  production  of 
hydrogen  in,  440. 

Electrolysis  of  water,  536. 

Electrolysis  to  make  hydrogen,  440. 

Electrolyte,  acid,  558,  562. 

Electrolyte,  addition  of  soaps  and  ferric 
oxide,  552. 

Electrolyte,  caustic  soda,  547,  552,  559, 
561,  571. 

Electrolyte,  caustic  potash,  559. 

Electrolyte,  mineral  oil  film  on,  561. 

Electrolyte,  potassium  carbonate,  541, 
550. 

Electrolyte,  potassium  tartrate,  562. 

Electrolyte,  sodium  tartrate,  562. 

Electrolyte,  sulphuric  acid,  544. 

Electrolyte,  use  of  citrates,  562. 

Electrolytic  addition  of  hydrogen,  3. 

Electrolytic  deposit  of  nickel,  57. 

Electrolytic  generation  of  hydrogen,  517. 

Electrolytic  nickel,  57. 

Electrolytic  Oxygen  and  Hydrogen  Asso- 
ciation, 603. 

Electrolytic  oxy-hydrogen  laboratories, 
578. 

Electrolytic  plant,  cost  of,  538. 

Electrolytic  plant,  equipment,  537. 

Electrolytic  platinum,  257. 

Electrolytic  reduction,  88,  275,  279. 


Electrolytic  reduction  of  unsaturated 
acids,  279. 

Electrolytic  system,  safety  of,  595. 

Electrolytically-derived  gases,  handling 
of,  590. 

Electrolyzer  of  Aigner,  558. 

Electrolyzer,  amalgmated,  558. 

Electrolyzer,  bipolar,  571,  588. 

Electrolyzer,  filter  press  type,  541,  559,, 
560,  570,  571,  575. 

Electrolyzer,  lanterns,  567. 

Electrolyzer  operating  cost,  569. 

Electrolyzer,  sectional  type,  575,  577. 

Electrolyzer  of  welded  sheet  iron,  554. 

Electrolyzer  without  diaphragm,  555. 

Elektrizitats-A.-G.-Vorm.  Schuckert  & 
Co.,  552. 

Elektro  Chemische  Werke,  112. 

Elgstrom,  337.  • 

Ellenberger,  446. 

Ellis,  1,  22,  23,  25,  26,  32,  34,  43,  53,  63, 
76,  90,  93,  96,.  106,  136,  137,  141,  142, 
144,  145,  146,  147,  149,  150,  160,  161, 
164,  168,  169,  174,  175,  177,  179,  185, 
186,  189,  197,  198,  209,  237,  238,  239, 
259,  281,  282,  283,  306,  331,  332,  333, 
335,  336,  340,  343,  348,  361,  397,  405, 
409,  411,  417,  422,  432,  448,  456,  476r 
480,  603,  675,  696. 

Ellis  butter-substitute  patent,  684. 

Ellis  electrolyzer,  570. 

Ellis  process  of  making  hydrogen,  482. 

Elsworthy,  467. 

Elworthy,  110,  167,  174,  448,  450,  467, 
491. 

Ely,  686. 

Emery,  411. 

Emulsification  of  oily  material  with 
milk,  332. 

Emulsion  for  blending  with  hydro- 
genated  oils,  357. 

Enderli,  168 

Enduli,  424. 

Engels,  444. 

Engler,  424. 

English  soap  trade,  359. 

Enzymes,  247. 

Equilibrium,  oleic  acid,  223. 

Erdmann,  8,  13,  19,  51,  109,  118,  120 
121,  122,  123,  124,  125,  128,  130,  133 


INDEX 


137,  138,  181,  184,  199,  201,  203,  205, 
206,  207,  208,  210,  211,  214,  215,  218, 
220,  221,  222,  223,  224,  271,  292,  400, 
406,643,661,682. 

Erdmann,  experimental  work  by,  213. 

Erdmann  on  Normann  patent,  212. 

Erlandsen,  337. 

Ernst,  247. 

Erucic  acid,  280,  285,  297,  300,  301,  315, 
440,  609. 

Erucic  acid,  .determination,  285. 

Erucic  acid  to  behenic  acid,  285. 

Esch,  29. 

Eschweger  soaps,  374,  387. 

Espil,  126,  127,  160,  175,  220. 

Essential  oils,  365. 

Essential  oils,  hydrogen  number  of,  255. 

Estabrook,  340. 

Esterbrook,  646. 

Ester  number,  395. 

Esterification,  Dreymann's  method,  92. 

Esterification  process,  92. 

Esterification  with  glycerine,  93. 

Esters,  332. 

Esters,  cinnamic,  260. 

Esters,  fatty,  52. 

Esters  for  making  hydrogen,  530. 

Ethane,  438. 

Ethyl  acetate,  86,  92,  280,  530. 

Ethyl  ester,  92. 

Ethyl  ester  of  linolenic  acid,  51. 

Ethyl  ester  of  linolic  acid,  51. 

Ethyl  ester  of  linseed  oil  fatty  acids,  51. 

Ethyl  ester  of  stearic  acid,  51. 

Ethyl  oleate,  90. 

Ethyl  stearate,  51. 

Ethylene,  58,  112,  143,  247,  420,  532, 
606,  611,  621. 

Ethylene  compounds,  269. 

Ethylene  derivatives,  114. 

Ethylene  hydrocarbons,  160. 

Eugenol,  86. 

Europe,  capacity  of  plants  in,  352. 

Europe,  production  of  linseed  oil  in,  352. 

European  hardening  plants,  399. 

Evans,  421. 

Expansion  of  hydrogenated  oils,  361. 

Explosion  arrester,  603. 

Explosion  by  evolution  of  gas,  265. 

Explosion  dangers,  169. 


Explosion  of  carbonyl  and  air,  233. 

Explosion  of  hardening  tank,  603. 

Explosion  of  nickel  carbonyl  vapor,  237. 

Explosions,  causes  of,  592. 

Explosions  of  oxygen,  602. 

Explosions,  possibility  of,  590. 

Explosions  when  compressing,  592. 

Explosive  mixtures  of  oxygen  and  hydro- 
gen, 601. 

Explosive  properties  of  nickel  compound,. 
230. 

Extraction  of  catalyzer,  214. 

Extraction  of  nickel  from  ores,  234. 

Eycken,  559. 

Fabris,  106,  116,  267. 

Fahrion,  105,  107,  256. 

Falciola,  85. 

Farmer,  33. 

Farnsteiner,  290. 

Fat,  beef,  355. 

Fat  having  the  melting-point  of  butter,, 

332. 

Fat,  lard-like,  58. 

Fat  mixture  for  preparing  soap,  364. 
Fat,  semi-solid,  632. 
Fat-soluble  growth  substances  of  beef 

fat,  355. 

Fat  splitting,  394,  398. 
Fat,  stuffing,  408. 
Fats  and  their  economical  use  in   the 

home,  340. 
Fats,  animal,  333. 
Fats,  liquid,  cause  shortening,  345. 
Fats,  low  grade,  328. 
Fatty  acid,  52,  67,  68,  83,  325,  363,  373, 

377,  380,  394,  398,  405,  408. 
Fatty  acid  and  ammonia,  84. 
Fatty  acid  anhydrides,  79. 
Fatty  acid  as  candle  material,  378. 
Fatty  acid,  cotton  oil,  298. 
Fatty  acid,  electrolytic  reduction  of,  280., 
Fatty  acid,  examination  of,  379. 
Fatty  acid,  high  content  of,  137. 
Fatty  acid,  hydrogenation,  280. 
Fatty  acid,  hydroxy,  313. 
Fatty  acid,  odor  of,  370. 
Fatty  acid  of  hardened  fish  and  whale 

oil,  395. 
Fatty  acid  of  sunflower  oil,  297. 


730 


INDEX 


Fatty  acid  produced  by  moisture,  140. 

Fatty  acid  separation  by  solvents,  408. 

Fatty  acid,  titre,  322. 

Fatty  alcohol,  284. 

Fatty  aromatic  amines,  84. 

Fatty  cleavage  reagent,  29. 

Fatty  esters,  52. 

Fatty  food  products,  method  of  making, 

346. 

Fatty  products  of  saponification,  379. 
Fay  and  Seeker,  112. 
Feeding  tests  of  hydrogenated  oils,  339. 
Feld,  94. 

Fels  Naphtha  Soap  Works,  382. 
Ferric  chloride,  273, 
Ferric  hydrate,  262. 
Ferric  hydroxide,  273. 
Ferric  oxide,  151,  512. 
Ferric  oxide,  hydrated,  452. 
Ferric  oxide  in  electrolyte,  552. 
Ferric  nitrate,  451,  455. 
Ferriferous  nickel  oxide,  impure,  230. 
Ferrite,  alkali,  458. 
Ferro-carbonyl  liquid,  233. 
Ferrosilicon,  533. 

Ferrosilicon  and  caustic  soda,  595. 
Ferrosilicon  with  soda-lime,  521. 
Ferroso-ferric  oxide,  502,  512. 
Ferrous  carbonate,  451,  502. 
Ferrous  oxalate,  151. 
Ferrous  sulphate,  454,  516. 
Fettraffinerie,  A.  G.,  406. 
Fibrous  material  in  making  catalyzer,  56. 
Fiersot,  550. 
Fierz,  237. 
Filling-in  fat  stock,  hardened  fish  oil  as. 

374. 

Filling,  soap,  375. 
Filter  press,  Shriver,  417. 
Filter  press  type  of  electrolyzer,  541,  559, 

560,  570,  571,  575. 
Filtration,  careless,  324. 
Filtration,  magnetic,  169. 
Filtration  to  remove  finely  divided  nickel, 

417. 
Finely   divided   nickel,    233,   248,   331, 

344. 

Finely  divided,  meaning  of,  624. 
Finely  divided  metal  as  catalyzer,  212. 
Pire  brick,  174,  434. 


First  disclosure  of  hydrogenation  of  oils 

in  a  liquid  state,  7. 
Firth,  268,  274. 
Fischer,  294,  550. 
Fischli,  184,  314. 

Fish  and  whale  oil,  properties  of,  395. 
Fish  meal,  350. 
Fish  oil,  25,  73,  83,  87,  147,  153,  155, 

248,  281,  301,  328,  329,  339,  340,  358, 

360,  362,  378,  390,  392,  394,  395,  396, 

398,  401,  405,  409,  411,  607,  609,  612. 
Fish  oil,  hardened,  285,  286,  287,  291, 

292,  295,  368,  372. 
Fish  oil,  hydrogenated,  338,  242. 
Fish  oil  in  edible  fats,  302. 
Fish  oil  in  margarine,  329. 
Fish  oils,  cost  of,  353. 
Fish  oils,  utilization  of,  349. 
Fixation  of  hydrogen,  271. 
Flake  white,  635,  675,  677,  695. 
Flaky  cobalt,  141. 
Flaky  iron,  505. 
Flake  nickel,  140,  219. 
Flash-back,  563. 
Flatting  paint  composition,  409. 
Flavor,  improvement  of,  348. 
Flavor  of  product,  319. 
Flavoring  compound,  332. 
Flax,  56. 

Flocculated  nickel  oxide,  218. 
Florolene,  691. 
Flour,  383. 
Flour  and  hard  fat  in  making  bread, 

341. 

Flour  and  hardened  oil,  646. 
Flour  and  powdered  hard  fat,  340. 
Flour-like  shortening  agent,  340. 
"  Fluffy  "  hardened  product,  321. 
Fluorides,  156. 

Fluorine,  complex  compounds  of,  155. 
Fluosilicic  acid,  256. 
Fluxes,  251. 
Foerster,  276. 
Foersterling,  519. 
Fokin,  101,  209,  221,  242,  249,  257,  275, 

297,  657,  665,  697. 

Food  compound  simulating  lard,  344. 
Food  elements,  355. 

Food  prepared  in  nickelware  vessels,  348. 
Food  product,  liquid,  354. 


INDEX 


731 


Food  value  of  hydrogenated  corn  oil, 

350. 

Food  value  of  hydrogenated  oil,  339. 
Foodstuffs,  content  of  nickel,  327. 
Ford,  435. 

Formaldehyde,  192,  255,  382,  423,  450. 
Formaldehyde,  reducing  effect  of,  205. 
Formalin,  55. 
Formate,  calcium,  446. 
Formate  in  place  of  hydrogen,  78. 
Formate  metallic,  78. 
Formate,  nickel,  48,  52,  79,  125,  130,  138, 

140,  147,  154,  179,  183,  192,  194,  198, 

200,  202,  224,  225,  227,  406,  437. 
Formate  reduction,  192. 
Formate,  zinc,  78,  79,  130,  140. 
Formates,  47,  108, 125,  153, 190,191,194. 
Formates,  making,  153. 
Formation  of  hydrides,  270. 
Formation  of  lactones,  285. 
Formation  of  nickel   by   overhardening, 

219. 
Formic  acid,  39,  140,  153,  194,  251,  280, 

419,  450. 

Formic  acid,  salts  of,  130. 
Formula  for  making  milled  soap  base, 

370. 

Formulas  for  lubricants,  403. 
Fortini,  295. 
Fortini's  test,  292. 
Forwood,  434. 
Fossil  meal,  131. 
Fourniols,  533. 
Fox,  411. 
Franck,  135,  255. 
Frank,  462,  463,  464,  467,  478. 
Frank-Linde-Caro  process,  62. 
Frank  purification  process,  597. 
Franke,  422. 
Frasch,  484. 
Frazer  generator,  588. 
Fredrikstad  plant,  360. 
Free  fatty  acid,  324,  351. 
Free  fatty  acids,  content  of,  282. 
Frerichs,  210. 
Fresenius,  149. 
Fresnaye,  530. 
Freundlich,  3. 
Fredricia,  337. 
Fry,  443. 


Fryer,  302,  303. 
Fuchs,  40,  187. 
Fullers'  earth,  10,  94,  159,  171,  224,  239, 

417. 
Fumaric  acid,  279,  280. 

Gaebel,  304. 

Galactose,  257. 

Galvanoplastic  process,  141. 

Gallic  acid,  530. 

Garbage  grease,  88. 

Garbage  grease  for  making  hydrogen, 

484. 

Garth,  284,  362,  371,  381. 
Garuti,  544,  591. 
Garuti  apparatus,  546. 
Gas,  coal,  240. 

Gas  cylinders,  finely  divided  iron  in,  592. 
Gas  cylinders,  oil  in,  592. 
Gas,  diffusion  of,  443. 
Gas,  freeing  from  carbon  dioxide,  599. 
Gas,  igniter,  251,  264. 
Gas,  inert,  169,  231. 
Gas,  measuring  system,  37. 
Gas,  producer,  446. 
Gas  Products  Association,  603. 
Gas  purification,  595. 
Gas  separator,  centrifugal,  467. 
Gas,  water,  232,  237,  241,  444,  620. 
Gases,  hydrogen,  containing,  232. 
Gasoline,  68,  418. 
Gasoline  from  crude  oil,  423. 
Gates,  325. 

Gautier,  450,  467,  502. 
Gauze,  wire,  456. 
Geeraerd,  589. 
Geisenberger,  473. 
Geitel,  197. 
Gelatin,  194,  247,  257. 
Gslatinous  aluminum  hydrate,  192. 
Gelatinous  silicon  hydrate,  192. 
Generating    hydrogen    by    electrolysis, 

536. 

Generation  of  electrical  energy,  516. 
George  Schicht,  A.-G.,  241,  402    . 
Gerard,  248. 
Gerhartz,  501. 

German  gas  regulations,  602. 
German  importation  of  fats,  349. 
German  pale  yellow  soap,  393. 


732 


INDEX 


German  utilization  of  fats,  349. 

Germania  Oelwerke,  362,  373,  387,  406. 

Germania  oil  works,  287. 

Germany  and  the  hydrogenation  process, 
80. 

Germany  and  the  whale  oil  question, 
331. 

Germany  and  use  of  hardened  whale  oil, 
339. 

Germany,  fats  in,  390,  398. 

Germany,  hydrogenation  in,  212. 

Gerum,  6. 

Ges  fur  Lindes  Eismaschinen,  600. 

Gheorghiu,  348. 

Giffard,  485. 

Gill,  338. 

Glaser,  126,  208. 

Glass,  256,  432. 

Glass  carrier,  119 

Glass  fragments  and  nickel,  176. 

Glass  wool,  135,  590. 

Glue,  428. 

Glue  solutions,  257. 

Glycerate,  nickel,  197. 

Glycerides,  mixed,  337. 

Glycerides  of  linoleic  acid,  transforma- 
tion to  olein,  415. 

Glycerides,  partial  saturation  of,  322. 

Glycerine,  32,  86,  186,  194,  197,  313, 
373,  394,  408,  600. 

Glycerine  containing  lyes,  370. 

Glycerine  content,  349. 

Glycerine  content  of  oils  and  fats,  method 
of  increasing,  348. 

Glycerine  determination,  313. 

Glycerine  enrichment  of  oil,  348. 

Glycerine  esterification,  93. 

Glycerine,  esterification  with,  32. 

Glycerine  oleate,  91. 

Glycerine,  removal  of,  365. 

Glycerine  soaps,  transparent,  375. 

Glycerol  content  of  hardened  fats,  313. 

Glycollates,  48. 

Godfrey,  341,  356. 

Gold,  246,  265,  276. 

Gold  leaf,  267. 

Gold-palladium,  277. 

Gold,  precipitated,  267. 

Gold  sol,  262. 

Goldenburg,  252. 


Goldschmidt,  2,  19,  443,  608,  612. 
Government  investigations  on    hydro- 

genated  oils,  326. 
Graff,  681. 
Graham,  269. 
Grained  soap,  371. 
Granite  surfaces,  11. 
Grape  seed  oil,  39. 
Graphite,  175,  411,  420. 
Grease  for  making  hydrogen,  484. 
Grease,  garbage,  88. 
Grease,  lubricating,  411. 
Green,  448. 

Green  hydrate  of  nickel,  617. 
Green  nickel  hydrate,  232. 
Green  nickel  oxide,  98. 
Greisheim-Elektron,  440,  444,  458,  525, 

595. 

Griffin's  apparatus,  581. 
Grignard,  221. 
Grimme,  292. 
Grinding  compound,  411. 
Groh,  257. 
Grossmann,  294. 
Griin,  89,  302. 
Griiner,  33,  61. 
Guayule  resin,  405. 
Guillien,  532. 
Gum,  121. 
Gum  arabic,  200,  246,  247,  250,  254,  257,. 

452,  600. 

Gum  tragacanth,  452. 
Gums,  varnish,  405. 
Gurney,  399. 
Gutbier,  268. 
Gypsum,  520. 

Haas,  189. 

Haber  process,  80. 

Hagemann,  95,  140,  167. 

Hajek,  380. 

Halla,  269. 

Haleco,  372. 

Halibut  oil,  411. 

Hall,  11,  331,  428. 

Haller,  11. 

Halliburton,  355. 

Halogens,  160,  164. 

Halogens,  determination  of,  316. 

Haiphen  reaction,  242,  697. 


INDEX 


733 


Halphen  test,  104,  285,  303,  317,  325, 
628,  639. 

Halske,  550,  600. 

Halter,  581. 

Hamburg,  107. 

Hamburger,  168. 

Hamlin,  533. 

Hammond's  control  apparatus,  603. 

Hand,  630. 

Hand,  decision  of  Judge,  700. 

Hanko,  647,  691. 

Hanus  method,  405. 

Hard  fat  from  peanut  oil,  250. 

Hard  soap,  demand  for,  352 

Hard  soaps,  made  by  hydrogenation, 
360. 

Hardened  castor  oil,  381 

Hardened  cotton  oil,  328. 

Hardened  fats,  capacity  for  holding 
water,  355. 

Hardened  fish  oil,  328. 

Hardened  fish  oil  as  substitute  for  tallow, 
374. 

Hardened  fish  oil  in  oleomargarine,  339. 

Hardened  fish  oil  in  soap,  378. 

Hardened  oil  and  flour,  646. 

Hardened  oil,  atomization,  342. 

Hardened  oil,  economy  of  using,  323. 

Hardened  oil,  edibility  of,  323,  326,  347. 

Hardened  oil  in  the  candle  industry,  398. 

Hardened  oil,  glycerine  content,  313. 

Hardened  oil,  hydrogen  in,  692. 

Hardened  oil,  keeping  properties  of,  337. 

Hardened  oil,  nickel  content  of,  328. 

Hardened  oil,  properties  and  uses  of,  352. 

Hardened  oil,  semi-solid,  632. 

Hardened  oil,  splitting  reagent,  30. 

Hardened  whale  oil,  chemical  composi- 
tion of,  314. 

Hardened  whale  oil  for  food,  330. 

Hardened  whale  oil  in  oleomargarine, 
339. 

Hardening  cottonseed  oil,  rate  of,  128. 

Hardening  curves,  219. 

Hardening  in  Europe,  399. 

Hardening,  instantaneous,  693. 

Hardening  linseed  oil  with  basic  nickel 
carbonate,  225. 

Hardening  linseed  oil  with  nickel  for- 
mate, 225. 


Hardening  of  linseed  oil  with  metallic 
nickel,  226. 

Hardening  plants  using  water  gas,  461. 

Hardening  process,  610. 

Hardening  sesame  oil  with  basic  nickel 
carbonate,  225. 

Hardening,  speed  of  reaction,  226. 

Hardening  tank  explosion,  603. 

Hardening  with  ammonia,  84. 

Hardening  with  aniline,  84. 

Hardening  with  hydrazine,  85. 

Hardening  with  trimethylamine,  84. 

Harmsen,  382. 

Harness  leather,  408. 

Hartl,  294. 

Hartmann,  6,  250,  264. 

Hauchecorne  test,  309. 

Hauser,  373. 

Hausamann,  129,  195,  198. 

Hausmann,  21. 

Hautefeuille,  270. 

Hazard-Flamand  apparatus,  564. 

Healthy  nickel,  271. 

Heat  decomposition  of  oils  to  yield  hy- 
drogen, 482. 

Heat  of  bromination,  101. 

Heat  on  hydrocarbons,  effect  of,  471. 

Heating  fatty  acids  with  water  under 
pressure,  89. 

Hebert,  402. 

Hefter,  1,  223,  294,  329. 

Hehner,  155,  163,  623,  629. 

Hehner  number,  295. 

Hehner's  statement,  617. 

Heim,  402. 

Heinemann,  260. 

Helbig,  532. 

Heller,  363,  373. 

Hembert  &  Henry  process,  447. 

Hemp,  56. 

Hemptinne,  3,  30,  83. 

Hendricks,  66. 

Henke,  457. 

Henry,  447. 

Henry's  law,  274. 

Hepburn,  588. 

Herforder,  7. 

Herman,  479. 

Herring  oil,  163,  392. 

Herford  oil  works,  212. 


734 


INDEX 


Herrings,  utilization  in  Germany,  350. 

Hertzog,  105. 

Herzman,  84. 

Hess,  264. 

Heterocyclic  compounds,  246. 

Hexahydrobenzene,  611. 

Hexahydrophthalic  acid,  264. 

Hexamethylene  hydrocarbons,  257. 

Heyl,  421. 

Higgins,  39,  47,  78,  88,  95,  110,  126,  130, 

140,  193,  194,  198,  406,  430. 
High  hydrogen  pressure,  19. 
High  pressure  apparatus,  52. 
High  tension  electric  discharge,  74,  435. 
Hildebrandt,  461. 
Hildesheimer,  143. 
Hills,  486. 
Hirt,  436. 
History  of  hydrogenation  at  Proctor  & 

Gamble's  665. 
Hlavati,  523. 
Hoehn,  82. 
Hofer,  424. 
Hofmann,  259. 
Hofstede,  260. 
Hoitsema,  270. 
Hokkaido,  392. 
Holbrook,  343. 
Holcgreber,  422. 
Holde,  439. 
Holmes,  339,  668 
Holt,  268,  269. 
Homfray,  274. 
Hooton,  511. 
Hoyer,  207. 
Huber,  302,  311. 
Huebl,  304. 
Huet,  329. 

Hugel,  281,  284,  286,  313,  326,  327. 
Human  consumption  of  hardened  oil, 

question  of,  347. 
Humphrey,  423. 
Humphreys,  64,  425. 
Huston,  11. 
Hydrate,  cobalt,  146. 
Hydrate,  copper,  146,  162. 
Hydrate,  hydrazine,  261. 
Hydrate,  lime,  446. 
Hydrate,  nickel,  109,  115,  131,  138,  146, 

147,  149,  153,  172,  186,  207,  232. 


Hydrate  of  nickel  and  copper,  55. 

Hydrated  non-basic  oxides,  262. 

Hydration  of  fatty  acids,  89. 

Hydrazine  hydrate,  85,  253,  261. 

Hydrazine,  reducing  power  of,  176. 

Hydride,  boron,  143. 

Hydride,  calcium,  520,  533,  595. 

Hydride,  cerium,  279. 

Hydride,  cobalt,  275. 

Hydride,  copper,  196. 

Hydride  for  making  hydrogen,  520. 

Hydride  nickel,  66,  693. 

Hydride,  nickel  oxide,  216. 

Hydride,  palladium,  269. 

Hydride,  platinum,  251. 

Hydride,  primary,  271. 

Hydride,  suboxide,  210. 

Hydrides,  formation  of,  270. 

Hydrides  in  catalyzers,  275. 

Hydrides,  metal,  275. 

Hydrides,  removal  of,  137. 

Hydrik  process,  523. 

Hydriodic  acid,  reduction  of  oleic  acid 
by,  2. 

Hydrobromic  acid,  160. 

Hydrocarbon  oils,  20. 

Hydrocarbons,  15,  110,   153,  231,  267, 
278,  611. 

Hydrocarbons  and  water  vapor,  472. 

Hydrocarbons,  catalyzer  for,  151. 

Hydrocarbons,  decomposition  of,  471. 

Hydrocarbons  for  making  hydrogen,  449. 

Hydrocarbons,  removal  of,  597. 

Hydrocarbon  oils,  treatment  with  hy- 
drogen, 10. 

Hydrocarbons,  treatment  with  steam,  21.. 

Hydrocarbons,  unsaturated,  250. 

Hydrochloric  acid,  113,  160,  223,  513. 

Hydrochloride,  platinum,  242. 

Hydrocyanic  acid,  165,  247. 

Hydrofluosilicic  acid,  256. 

Hydrogen,  104. 

Hydrogen  absorption,  272. 

Hydrogen  absorption  by  limonene,  269. 

Hydrogen,  absorption  by  nickel,  60. 

Hydrogen,    absorption    by    petroleum 
430. 

Hydrogen,  action  on  metal,  270. 

Hydrogen,  action  on  phytosterol,  284. 

Hydrogen  added  to  oil,  695. 


INDEX 


735 


Hydrogen  addition,  mechanism  of,  265. 
Hydrogen,  addition  to  fatty  oil,  282. 
Hydrogen,  amount  for  cocoanut,  olive, 

corn  oil,  tallow,  oleic  acid,  439. 
Hydrogen,  analysis  of,  476. 
Hydrogen  and  carbon  black,  480,  481. 
Hydrogen  and  lampblack,  473. 
Hydrogen  and  nitrogen  mixtures,  532. 
Hydrogen  and  oxygen,  combination  of, 

275. 

Hydrogen  and  oxygen,  union  of,  247. 
Hydrogen  and  sodium  silicate,  530. 
Hydrogen,  as  reducing  gas,  210. 
Hydrogen  at  high  pressures,  vessels  for, 

529. 
Hydrogen,  barium  hydrate  for  making, 

458. 

Hydrogen  bubbling  process,  25. 
Hydrogen  by  action  of  acids  on  metals, 

515. 

Hydrogen  by  action  of  solar  rays,  501. 
Hydrogen  by  arc  decomposition,  558. 
Hydrogen  by  brine  electrolysis,  440. 
Hydrogen  by  Bruno  process,  517. 
Hydrogen  by  Burdett  system,  563. 
Hydrogen  by  catalytic  absorption,  250. 
Hydrogen  by  catalytic  action,  451. 
Hydrogen  by  decomposition  of  hydro- 
carbons, 534. 

Hydrogen  by  Dempster  system,  507. 
Hydrogen  by  diffusion,  450,  467,  531. 
Hydrogen  by  electrolysis,  518,  534. 
Hydrogen  by  electrolysis  of  water,  536. 
Hydrogen   by   heating   zinc   dust   with 

hydrated  lime,  526. 
Hydrogen  by  I.  O.  C.  system,  568. 
Hydrogen  by  iron  alloys,  502. 
Hydrogen  by  Linde  process,  534. 
Hydrogen  by  liquefaction,  480. 
Hydrogen  by  passing  steam  over  coke, 

447. 
Hydrogen     by    process    of    Improved 

Equipment  Co.,  512. 
Hydrogen,  by-product,  440. 
Hydrogen  by  Schuckert  system,  551. 
Hydrogen  by  the  action  of  steam  on 

heated  metal,  485. 
Hydrogen    by    the    decomposition    of 

hydrocarbons,  471. 
Hydrogen  by  use  of  alloys,  525. 


Hydrogen  by  use  of  barium  sulphate, 
535. 

Hydrogen  by  use  of  molten  zinc,  532. 

Hydrogen  by  use  of  scrap  iron,  533. 

Hydrogen  by  use  of  steam  and  carbon, 
527. 

Hydrogen  carriers,  275. 

Hydrogen,  catalyzer  for  making,  479. 

Hydrogen,  catalyzers  in  making,  444. 

Hydrogen,  classification  of  methods,  44  U 

Hydrogen  containing  carbon  monoxide, 
40,  42. 

Hydrogen-containing  compounds,  270. 

Hydrogen-containing  gas,  448. 

Hydrogen-containing  gases,  232. 

Hydrogen-containing  metals,  265. 

Hydrogen  containing  moisture,  596. 

Hydrogen  contaminated  with  air,  592. 

Hydrogen  conveyors,  active,  212. 

Hydrogen,  cost  of,  476,  508,  515,  534. 

Hydrogen  cylinders,  440,  533. 

Hydrogen,  danger  of  explosion,  169. 

Hydrogen,  deodorizing  by,  87. 

Hydrogen  developed  by  recovered  cata- 
lyst, 215. 

Hydrogen  dioxide,  33,  247. 

Hydrogen,  dry,  127. 
v  Hydrogen,  effect  of  pressure,  170. 

Hydrogen,  electrolytic  addition  of,  3. 

Hydrogen  electrolyzers,  control  of,  585. 

Hydrogen,  fixation  of,  271. 

Hydrogen  for  military  balloons,  533. 

Hydrogen  for  military  purposes,  80. 

Hydrogen,  formation  of  carbon  in  mak- 
ing, 510. 

Hydrogen  free  from  carbon  monoxide, 
510. 

Hydrogen  from  acetylene,  472. 

Hydrogen  from  aluminum  and  caustic 
soda,  519,  523,  532. 

Hydrogen    from    bitumen    and    shale, 
473. 

Hydrogen  from  calcium  hydride,  520. 

Hydrogen  from  carbon  dioxide,  separa- 
tion of,  466. 

Hydrogen  from  catalyzer,  210. 

Hydrogen  free  from  catalyzer  poisons, 
532. 

Hydrogen  from  coke,  447. 

Hydrogen  from  ferrosilicon,  521. 


736 


INDEX 


Hydrogen  from  ferrosilicon  and  steam, 

522. 

Hydrogen  from  garbage  grease,  484. 
Hydrogen  from  Garute  generator,  544. 
Hydrogen  from  hydrocarbons,  449. 
Hydrogen  from  hydrocarbons  and  steam, 

476,  479. 

Hydrogen  from  illuminating  gas,  476. 
Hydrogen  from  iron  and  carbon  dioxide, 

517. 
Hydrogen  from  iron  and  hydrochloric 

acid,  515. 

Hydrogen  from  iron  briquettes,  501. 
Hydrogen  from  methane,  480. 
Hydrogen  from  molten  metal,  501. 
Hydrogen  from  natural  gas,  438,  478, 

484. 

Hydrogen  from  petroleum,  424,  478,  484. 
Hydrogen  from  Schmidt  generator,  541. 
Hydrogen  from  silicides,  519. 
Hydrogen  from  sodium,  519. 
Hydrogen  from  steam.  485. 
Hydrogen  from  steam  and  iron  at  high 

pressure,  528. 
Hydrogen  from  sulphuric  acid  s..nd  iron, 

generation  of,  516. 
Hydrogen    from    waste    liquor   sludges, 

531. 

Hydrogen  from  water  gas,  444. 
Hydrogen  from  zinc,  80,  515. 
Hydrogen  from  zinc  and  lime,  520. 
Hydrogen  gas  in  aeronautics,  534. 
Hydrogen,  gases  containing,  144. 
Hydrogen      generation,      miscellaneous 

methods,  519. 

Hydrogen  given  off  by  cataylzer,  206. 
Hydrogen,  handling  of,  415. 
Hydrogen  high-pressure  apparatus,  600. 
Hydrogen,  high  pressure  process,  513. 
Hydrogen  impurities,  493. 
Hydrogen  in  electrolytic  oxygen,  601. 
Hydrogen   in   gaseous   mixtures,   deter- 
mination of,  314. 

Hydrogen,  iron  and  steam  method^  534. 
Hydrogen  leakage,  415. 
Hydrogen,  lime  for  making,  457. 
Hydrogen,  nascent,  271,  273,  274,  437. 
Hydrogen  number,  50,  51,  101. 
Hydrogen  number,  determination  of,  306. 
Hydrogen  number  of  essential  oils,  255. 


Hydrogen,  obtaining  pure,  488. 

Hydrogen,  occluded,  132. 

Hydrogen,  occlusion  of,  265. 

Hydrogen  on  metallic  solutions,  276. 

Hydrogen,  partial  reduction  of  iron  in 
making,  486. 

Hydrogen  per  ampere  hour,  536. 

Hydrogen,  per  cent  in  hardened  oil,  692. 

Hydrogen  per  ton  of  oil,  107. 

Hydrogen  phosphide,  14,  610. 

Hydrogen,  phosphoretted,  231. 

Hydrogen  plant,  cost  of,  441. 

Hydrogen  plants,  stationary  and  port- 
able, 595. 

Hydrogen,  precautions  in  making,  512. 

Hydrogen,  preheated,  40. 

Hydrogen,  pressure  of,  in  hardening,  85. 

Hydrogen  problem  in  oil  hardening,  439. 

Hydrogen  processes  devised  by  Messer- 
schmitt,  490. 

Hydrogen  producer,  use  of  lime  in,  476. 

Hydrogen  producing,  437. 

Hydrogen  purification,  467,  488,  595. 

Hydrogen,  purification  by  absorption, 
467. 

Hydrogen,  purification  by  carbide,  597. 

Hydrogen,  rate  of  absorption,  71. 

Hydrogen,  reduction  in  solution  by,  170. 

Hydrogen,  replacement  of  carbon  mon- 
oxide, 444. 

Hydrogen  requirements  per  ton  of  fat, 
439. 

Hydrogen,  solubility  in  metals,  265. 

Hydrogen  standards,  603. 

Hydrogen,  steel  alloys  to  contain,  529. 

Hydrogen  storage  tanks,  594. 

Hydrogen,  strong  current  of,  620,  626. 

Hydrogen  sulphide,  15,  113,  163,  165, 
166,  208,  231,  318,  433,  434,  443,  455, 
487,  609,  615,  618,  620. 

Hydrogen  sulphide,  removal  of,  478. 

Hydrogen,  sulphur  and  arsenic  in,  163. 

Hydrogen,  supply  of,  440. 

Hydrogen  transfer  by  gas  holders,  76. 

Hydrogen  transfer  by  platinum  metals, 
269. 

Hydrogen,  transference  of,  271. 

Hydrogen,  use  of  alkali  ferrite,  458. 

Hydrogen,  use  of  copper  and  iron,  504. 

Hydrogen,  use  of  esters,  530. 


INDEX 


737 


Hydrogen,  use  of  manganese  ores,  495. 
Hydrogen,  use  of  sulphides,  511. 
Hydrogen,  use  of  water  gas,  441. 
Hydrogen,  using  alloys  of  iron,  499. 
Hydrogen,  using  sodium  bisulphate,  517. 
Hydrogen  value  of  organic  compounds, 

297. 

Hydrogen,  washing  with  water,  488. 
Hydrogen,  water  in,  166. 
Hydrogen    with    small    percentages    of 

oxygen,  602. 

Hydrogenated  animal  fats,  242. 
Hydrogenated  butter  fat,  337. 
Hydrogenated  corn  oil,  242,  335. 
Hydrogenated   castor  oil  as   insulator, 

409. 

Hydrogenated  corn  oil,  350. 
Hydrogenated  edible  oils,   patents  on, 

331. 
Hydrogenated  fat  compared  with  butter, 

338. 
Hydrogenated  fat,  edibility  of,  323,  326, 

347. 

Hydrogenated  fat  in  butter  fat,  318. 
Hydrogenated  fat  in  the  manufacture  of 

bread,  341. 
Hydrogenated  fat,  method  of  purifying, 

350. 

Hydrogenated  fat,  properties  of,  290. 
Hydrogenated  fatty  acid,  377. 
Hydrogenated  fish  oil,  242,  338. 
Hydrogenated    food    product     industry 

631. 

Hydrogenated  lard  compound,  321. 
Hydrogenated  linseed  oil,  387. 
Hydrogenated  linseed  oil  in  white  soap, 

388. 
Hydrogenated  oil,  analytical  constants 

of,  281. 
Hydrogenated  oil  and  baking  powder, 

343. 

Hydrogenated  oil  and  pulverulent  mate- 
rial, 411. 

Hydrogenated  oil  as  a  powder,  342. 
Hydrogenated  oil,  ash  of,  294. 
Hydrogenated  oil,  atomization,  342. 
Hydrogenated  oil,  color  reactions,  293. 
Hydrogenated  oil,  detection  of  nickel  in, 

339. 
Hydrogenated  oil,  digestibility  of,  338. 


Hydrogenated  oil,  edible,  319. 
Hydrogenated  oil,  expansion  of,  361. 
Hydrogenated  oil,  glycerine  content,  313. 
Hydrogenated  oil,  harmless,  339. 
Hydrogenated  oil,  hydrogen  in,  692. 
Hydrogenated  oil  in  butter  fat,  detection 

of,  297. 
Hydrogenated  oil,  keeping  qualities  of, 

337,  340,  411. 

Hydrogenated  oil,  partially,  308. 
Hydrogenated  oil  patent  litigation,  605. 
Hydrogenated  oil,  sale  of,  635. 
Hydrogenated  oil,  semi-solid,  632. 
Hydrogenated  oil,  tests  for,  288,  302. 
Hydrogenated   oil,    utilization   in   soap 

making,  358. 

Hydrogenated  olive  oil,  242. 
Hydrogenated  peanut  oil,  286,  290,  291, 

294. 

Hydrogenated  rosin,  403. 
Hydrogenated  rosin  in  varnishes,  403. 
Hydrogenating  by  Lessing  process,  240. 
Hydrogenating  coal,  431. 
Hydrogenating,  effect  of  glycerine,  32. 
Hydrogenating  equipment,  508. 
Hydrogenating  in  presence  of  solvents, 

67. 
Hydrogenating  oleic  acid  in  presence  of 

alkali,  79. 

Hydrogenation,  acceleration  of,  39. 
Hydrogenation  apparatus  for  laboratory, 

76. 

Hydrogenation  at  high  pressures,  175. 
Hydrogenation,  batch  method,  643. 
Hydrogenation   beyond    titre   required, 

333. 
Hydrogenation,   bubbling  process,   620, 

626. 

Hydrogenation  by  catalytic  action,  5. 
Hydrogenation  by  means  of  nickel  oxide 

and  metallic  nickel,  213. 
Hydrogenation  by  nickel  carbonyl,  207. 
Hydrogenation   by   use   of   chloride   of 

mercury,  144. 

Hydrogenation,  catalyzer  poisons,  223. 
Hydrogenation  Co.,  661. 
Hydrogenation,  continuous  method,  643. 
Hydrogenation  curves,  101,  155,  226. 
Hydrogenation  dependent  on  cheap  hy- 
drogen, 595. 


738 


INDEX 


Hydrogenation,  effect  of  pressure,  89. 

Hydrogenation,  effect  of  water,  226. 

Hydrogenation,  end  of,  633. 

Hydrogenation,  history  of,  654. 

Hydrogenation  in  Germany,  212. 

Hydrogenation  in  solution,  210. 

Hydrogenation  in  solvents,  187,  280. 

Hydrogenation,  instantaneous,  23,  693. 

Hydrogenation,  Lewkowitsch's  failure, 
617. 

Hydrogenation  of  benzol,  270. 

Hydrogenation  of  butter,  lard  and  oleo- 
margarine, 660. 

Hydrogenation  of  carbon  compounds, 
152. 

Hydrogenation  of  cholesterol,  283. 

Hydrogenation  of  cottonseed  oil,  incom- 
plete, 317. 

Hydrogenation  of  fatty  acids,  280. 

Hydrogenation  of  Japanese  fish  oil,  137. 

Hydrogenation  of  oil  by  passage  through 
a  centrifuge,  21. 

Hydrogenation  of  oils  containing  the 
hydroxyl  group,  38. 

Hydrogenation  of  oils  in  liquid  state,  7. 

Hydrogenation  of  oleic  acid,  80. 

Hydrogenation  of  oleic  acid  in  a  vapor- 
ized state,  26. 

Hydrogenation  on  color  tests  of  oils,  285. 

Hydrogenation  of  petroleum,  154,  418. 

Hydrogenation  of  the  benzol  ring  by 
nickel,  175. 

Hydrogenation,  partial,  96. 

Hydrogenation  plants,  European,  399. 

Hydrogenation  plants  using  water  gas, 
461. 

Hydrogenation  practice,  412. 

Hydrogenation  process,  610. 

Hydrogenation  process,  cyclic,  22. 

Hydrogenation  process  of  Lane,  82. 

Hydrogenation,  products  of,  105,  292. 

Hydrogenation,  progressive,  663. 

Hydrogenation,  selective,  25,  97. 

Hydrogenation,  size  of  apparatus,  100. 

Hydrogenation,  speed  of  reaction,  226. 

Hydrogenation  temperature,  39,  619. 

Hydrogenation,  use  of  carefully  dried  oil, 
220. 

Hydrogenation,  use  of  formic  acid,  140, 
194. 


Hydrogenation,  use  of  stirrer,  620,  626, 

Hydrogenation,  value  of,  620. 

Hydrogenation  with  carbonyl,  239. 

Hydrogenation  with  charcoal  catalyzer, 
149. 

Hydrogenation  with  dried  oil,  140. 

Hydrogenation  with  formic  acid,  251. 

Hydrogenation  with  nickel  carbonyl, 
177. 

Hydrogenation  with  nickel,  results  ob- 
tained by,  271. 

Hydrogenation  without  a  catalyst,  87. 

Hydrogenator  for  laboratory  use,  53. 

Hydrogenit  process,  521. 

Hydrogenite,  533,  595. 

Hydrogenized  fats  for  food,  669. 

Hydroil,  Ltd.,  107,  208. 

Hydrolecithin,  323. 

Hydrolith,  533. 

Hydrosol,  palladium,   264. 

Hydrosols,  207. 

Hydrosols,  platinum,  249. 

Hydrosulphite,  sodium,  273. 

Hydroxide,  ferric,  273. 

Hydroxide,  nickel,  202. 

Hydroxy  fatty  acids,  19,  84,  313. 

Hydroxy  stearic  acid,  3,  440. 

Hydroxyl  group,  313. 

Hydroxyl  group,  reduction  of,  313. 

Hydroxyl  number  of  hardened  oil,  284. 

Hydroxyl  value,  309. 

Hydroxylamine,  250. 

Hyland,  308. 

Hypogeic  acid,  291,  380. 

Hypophosphite,  nickel,  137. 

Hypophosphite,  sodium,  137. 

Hypophosphites,  174. 

Igniter,  gas,  251,  264. 

Ignition  catalyst,  167. 

Ignition  catalyzer,  251,  264. 

Illuminants  in  oil  gas,  424. 

Illuminating  gas,  433,  620. 

Illuminating  gas,  hydrogen  from,  476. 

Imbert,  2. 

Importation  of  fats  by  Germany,  349. 

Improved  Equipment  Co.,  512. 

Impurities  in  fatty  oils,  354. 

Impurities  in  oil,  211. 

Inaugural  dissertation  of  Bedford,  50. 


INDEX 


739 


Indene,  116. 

Index  of  refraction,  281,  282,  287,  292. 

Inert  carriers,  249. 

Inert  gas,  169,  171,  194,  231. 

Inert  gas,  use  of,  351. 

Indigo  white,  87. 

Inductor,  48. 

Industria  saponica,  208. 

Influence  of  time  on  progress  of  reduc- 
tion, 28. 

Infusorial  earth,  58,  98,  187,  519. 

Injector  nozzles,  72. 

Injector  system,  36. 

Instantaneous  hydrogenation,  23. 

Institute  of  Hygiene,  347. 

Institution  of  Petroleum  Technologists, 
428. 

Insulating  compounds,  358. 

Insulating  material,  84. 

Insulation,  359. 

Insulation  from  castor  oil,  409. 

Internal  combustion  engines,  hydrogen 
from,  480. 

International  Oxygen  Co.,  565,  571. 

International  Wasserstoff,  595. 

Internationale  Wasserstoff,  A.-G.,  496. 

Iodide,  silver,  273. 

Iodine,  113,  160,  162,  164,  419,  443. 

Iodine,  cheap  supply  of,  2. 

Iodine  number,  101,  155,  201,  215,  224, 
225,  287,  289,  290,  292,  295,  297:  304, 
309,  314,  317,  333,  357,  360,  362,  379, 
381,  392,  395,  397,  398,  424,  617,  655, 
659,  660,  663,  664,  692,  695,  701. 

Iodine  number  of  oleic  acid,  28. 

Iodine  number,  reduction  of,  281. 

Iodine  number  time  curves,  102. 

Iodine,  purifying  solution,  596. 

Iodine-sulphuric  acid,  292. 

Iodine  value,  345. 

Iodine  values  of  Kream  Krisp,  694. 

Ipatiew,  6,  19,  40,  108, 112, 116,  117, 122, 
126,  170,  209,  220,  226,  424. 

Iridium,  34,  250,  261,  264,  275,  600. 

Iron,  106,  146,  152,  175,  190,  208,  230, 
246,  248,  265,  270,  276,  279,  294,  379, 
404,  422,  423,  426,  429,  430,  432,  437, 
438,  449,  451,  455,  504,  531,  605,  609, 
611,  613,  615,  618,  621,  628. 

Iron  alloys,  499. 


Iron  alloys  for  making  hydrogen,  502. 

Iron-aluminum,  502. 

Iron  and  carbon  dioxide,  517. 

Iron  and  sulphuric  acid,  595. 

Iron  arc,  62. 

Iron  bars,  506. 

Iron  borings,  485. 

Iron  briquettes,  501. 

Iron,  caking  of,  491. 

Iron  carbide,  502. 

Iron  carbonate,  502. 

Iron,  catalytic  activity  of,  137. 

Iron  catalyzer,  52. 

Iron  chloride,  513. 

Iron-copper,  502. 

Iron-copper  couple,  459. 

Iron,  effect  of  sulphur  on,  485. 

Iron,  fatty  acid  salts,  193. 

Iron  filings,  137,  428,  498,  500. 

Iron,  finely  divided,  496. 

Iron,  finely  divided  in  gas  cylinders,  592. 

Iron  flakes  for  making  hydrogen,  505. 

Iron  formate,  191. 

Iron,  fritting  of,  499. 

Iron  hydrate,  264. 

Iron,  in  making  hydrogen,  448,  528. 

Iron-lead,  502. 

Iron,  molten,  501. 

Iron  netting,  58. 

Iron  nitrate,  146,  434. 

Iron  on  asbestos,  485. 

Iron  ore  briquettes,  502. 

Iron  ore,  sintering  of,  492. 

Iron,  organic  salts  of,  47,  130,  194. 

Iron  oxalate,  452,  502. 

Iron  oxide,  151,  167,  199,  402,  425,  426, 

448,  452,  455,  457,  501. 
Iron  oxide  catalyzer,  21. 
Iron  oxide  in  electrolyte,  552. 
Iron  oxide,  removal  of,  490. 
Iron,  partial  reduction,  486. 
Iron  protoxide,  513. 
Iron  pyrites,  486,  511. 
Iron  pyrites  waste,  use  of,  496. 
Iron,  pyrophoric,  592. 
Iron,  reaction  of  steam  with,  485. 
Iron,  reduced,  166. 
Iron,  revivication  of,  486. 
Iron  salts,  486. 
Iron  scrap,  509. 


740 


INDEX 


Iron  scrap,  percolation  of  acid  through, 

517. 

Iron-silver  couple,  459. 
Iron,  sintering  of,  507. 
Iron  soap,  129. 
Iron  sponge,  life  of,  594. 
Iron-sponge  steam  process,  440. 
Iron-sponge  steam  processes  of  making 

hydrogen,  485. 
Iron,  spongy,  505. 
Iron-steam  process,  595. 
Iron  sulphate,  21,  516. 
Iron  sulphide,  485. 
Iron  tartrate,  151. 
Iron-vanadium,  502. 
Iron- wire,  267. 
Iso  butyl  oleate,  90. 
Iso  eugenol,  86. 
Iso-oleic  acid,  79,  379. 
Isopentane,  116. 
Itaconic  acid,  280. 
Ittner,  93,  150,  390. 
Iwag  system,  496. 

Jackstones,  430. 

Jaffe,  300,  309. 

Jakowlew,  6. 

Janko,  302. 

Japanese  fish  oil,  hydrogenation  of,  137. 

Japanese  sardine  oil,  285. 

Japan  wax  soaps,  129. 

Japanese  wood  oil,  275. 

Japanned  leather,  407. 

Jaquet,  264. 

Jaubert,  104,  106,  511,  520,  521,  524, 

530,  588,  595. 
Jaubert  Method,  501. 
Jaubert's  process,  533. 
Java  citronella  oil,  376. 
Jenkins,  617. 
Jerzmanowski,  446. 
Jewel  compound,  691,  695. 
Jewel  compound  of  Swift  &  Co.,  687. 
Jobling,  105,  108. 
Jolicard,  437. 
Jones,  247. 
Jones  cell,  588. 
Joslin,  323,  350. 
Joukoff ,  279. 
Jouve,  467. 


Jurgens,  313. 
Jurisch,  276,  279. 
Jute,  56. 
Jutol,  363. 
Jutolin,  363. 

Kadt,  37,  40,  129. 

Kahlbaum's  nickel  oxide,  201,  214. 

Kalle  &  Co.,  254,  255. 

Kalmus,  112. 

Kalnin,  79. 

Kambara  earth,  311. 

Kamps,  20,  43. 

Kandel,  363. 

Kandelin,  363. 

Kandetil,  363. 

Kandorit,  363. 

Kansas  University,  350. 

Kaolin,  173,  275. 

Kaolin,  water  content,  effect  of,  276. 

Karite,  401. 

Karl,  248. 

Karplus,  167. 

Kast,   128. 

Kato,  581. 

Katz,  314. 

Kausch,  534. 

Kaya  oil,  336. 

Kayser,  15,  106,  131,  132,  147,  156,  212, 

633,  643,  650,  651,  652,  663,  666,  671, 

677,  697,  703. 

Kayser,  history  of,  661,  671. 
Kayser  kieselguhr  catalyzer,  131. 
Kayser  process,  663. 
Keebler,  356. 

Keeping  properties  of  hardened  oils,  337. 
Keeping  qualities,  411. 
Keeping  qualities  of  hardened  fat,  326. 
Keeping  qualities  of  liquid  oil,  354. 
Kelber,  164,  187,  194,  304,  316. 
Kelp,  2. 

Keratin,  262,  263. 
Kern,  273. 
Kerosene,  422,  432. 
Kerr,  296,  308. 
Kerzenit,  363. 
Kessener  method  of  producing  hydrogen, 

531. 

Ketones,  160,  271,  423. 
Kettle,  nickel,  327. 


INDEX 


741 


Keutgen,  330,  331. 

Kieselguhr,  49,  58,  98, 109, 131, 133,  135, 
139,  140,  147,  158,  176,  177,  192,  198, 
206,  241,  254,  344,  349,  404,  672,  673, 
693,  701,  703. 

Kieselguhr  as  a  carrier  for  nickel  cata- 
lyzer, 16. 

Kieselguhr,  purified,  211. 

Killing,  264. 

Kimura,  58,  171,  600. 

Klimont,  105,  338,  339. 

Knapp,  287,  295,  337. 

Knorr,  318. 

Knorre,  394. 

Knotte,  262. 

Knowles,  600. 

Knowles  Oxygen  Co.,  361. 

Knowles  purifying  system,  597. 

Kohlenpulver,  149. 

Kohman,  341,  356. 

Kolbe,  5. 

Korevaar,  279. 

Krafft,  377. 

Kream-Krisp,  630,  693. 

Kream-Krisp,  composition  of,  694. 

Krebitz  process,  365. 

Kreis,  286,  309. 

Krist,  402. 

Kritolit,  363. 

Krumhaar,  265. 

Krunotin,  363. 

Krutol,  363. 

Krutolin,  363,  383,  399. 

Krutello,  363. 

Kuess,  3. 

Laboratory  apparatus  of  Voswinckel,  52. 

Laboratory  hydrogenation  apparatus,  76. 

Laboratory  hydrogenator,  53. 

Lach,  382. 

Lackey,  350,  410. 

Lactate,  titanium,  154. 

Lactates,  47,  108. 

Lactic  acid,  salts  of,  130. 

Lactones,  79. 

Lactones,  formation  of,  285. 

Lahousse  barium  sulphide  process,  526. 

L'Air  liquide,  469. 

Lake,  608,  612. 

L' Aluminum  Francois,  174. 


Lamp  black,  473. 

Lamplough,  21,  424,  429. 

Landis,  536. 

Lane,  82,  171. 

Lane  hydrogen  process,  487. 

Lane  process,  486. 

Lane  process,  modified,  512. 

Lang,  339,  668. 

Langbein,  325. 

Langer,  110,  229,  232,  237,  448. 

Langer  and  Mond,  111. 

Lanterns  on  electrolyzers,  567. 

Lanthanum  oxide,  119. 

La  Peyrouse,  85. 

Lard,  309,  310,  384,  398,  409,  647,  660. 

Lard  compound,  96,  319,  701. 

Lard    compound,    change   in    color   on 

standing,  335. 
Lard  compound,  demand  for,  in  United 

States,  352. 

Lard  compound  production,  319. 
Lard  compound,  stringy,  675. 
Lard  consistency,  product  of,  346. 
Lard  cooler,  320. 
Lard-like  fat,   incompletely    hydrogen- 

ated,  345. 

Lard-like  fats,  58,  678. 
Lard-like  products,  333,  632,  696. 
Lard,  physical  appearance,  679. 
Lard,  rancid,  308. 

Lard  substitute,  production  of,  319,  322. 
Lard  substitutes,  701. 
Larsen,  586. 
Latchinoff,  537. 

Lather-forming  qualities  of  soap,  365. 
Lathering  properties,  377. 
Lathering  properties  of  milled  soaps,  370. 
Lathering  properties  of  soap,  380. 
Lathering  properties  of  talgol  mixture, 

367. 

Lathering  qualities,  372,  396. 
Laundry  soaps,  369,  374. 
Laundry  soaps,  hardened  fish  oils  in,  368. 
Lavender  oil,  377. 
Leach,  673. 

Lead,  153,  246,  248,  254,  265,  379,  502. 
Lead  carbonate,  530. 
Lead  catalyzer,  21. 
Lead  chlorate,  273. 
Lead,  effect  on  platinum,  243. 


742 


INDEX 


Lead,  electrodes,  544. 

Lead,  molten,  267,  430. 

Lead  nitrate,  456. 

Lead  oleate,  164. 

Lead  oxide,  162,  402,  421,  448,  455,  501, 

530. 

Lead  stearate,   164. 
Lead,  sulphide,  530. 
Leaf  lard,  96. 
Leather  belting,  408. 
Leather,  harness,  408. 
Leather  industry,  405. 
Leavened  bread,  356. 
Leavening  composition,  343. 
Leavening  ingredients,  343. 
Le  Blanc  process,  515. 
Lecithin,  323,  332,  357. 
Leffer,  21. 
Lehmann,  125,  249,  258,  304,  324,  326, 

327,  347. 
Leimdorfer,  170,  292,  326,  350,  358,  368, 

369. 

Lelarge,  592. 

"  Lengthening  "  of  soap,  383. 
Leprince,    7,   123,    125,  207,  212,   351, 

372. 

Lepsius,  441,  446. 
Leroy,  559. 
Leslie,  430. 
Lessing,  41,  104,  239. 
Lever  Bros.,  211,  611. 
Levi,  446. 
Levin,  560,  571. 
Levin  generator,  577. 
Levinstein,  401. 
Lewers,  686. 
Lewes  process,  485. 
Lewkowitsch,  1,  281,  285,  314,  354,  617, 

620,  626. 
Lieber,  330. 
Liebig,  251. 
Liebmann,  54,  56,  146,  612,  615,  617, 

624,  629. 

Light  oils,  production  of,  426. 
Lime,  428. 

Lime  and  water  gas,  594. 
Lime  as  a  flux,  476. 
Lime,  hydrated,  446. 
Lime,  in  making  hydrogen,  444,  445. 
Lime,  recovery  of,  446. 


Limonene,  absorption  of  hydrogen  by, 

269. 

Linde,  439,  470. 
Linde-Caro  process,  43,  241. 
Linde  Eismachinen,  A.-G.,  463. 
Linde-Frank-Caro,  595. 
Linde-Frank-Caro  system,  464. 
Linde  hydrogen  apparatus,  465. 
Linde  process,  534. 
Linde  system,  461. 
Lindt,  296. 
Liniments,  410. 
Linoleate,  nickel,  130,  138. 
Linoleic  acid,  89,  280,  287,  289,  301,  380, 

439,  609. 

Linoleic  and  linolenic  group,  333. 
Linoleic  compounds,  322. 
Linolenic  acid,  280,  289,  325,  380,  393, 

439. 

Linolenic  acid,  ethyl  ester  of,  51. 
Linolenic  anilides,  84. 
Linolenic  compound,  322. 
Linoleum  industry,  353. 
Linolic  acid,  287,  345,  393,  609. 
Linolic  acid,  ethyl  ester  of,  51. 
Linolin,  97,  652,  653,  654,  692,  694,  701, 

706. 

Linolith,  387,  388,  398,  399. 
Linseed  oil,  12,  39,  52,  89,  105,  122,  139, 

154,  155,  156,  181,  200,  201,  205,  213, 

215,  216,  217,  218,  223,  224,  225,  242, 

275,  282,  283,  301,  310,  355,  361,  387, 

393,  396,  398,  401,  406,  607,  609,  615, 

657,  658. 

Linseed  oil  fatty  acids,  50,  297. 
Linseed  oil  soap  formulas,  388. 
Linseed  oil,  supply  of,  352. 
Lipocromes,  637. 
Liquid,  effect  on  catalyzer,  13. 
Liquid  fats  cause  shortening,  345. 
Liquid  hydrocarbons,  15. 
Liquid  hydrogenated  oil,  354. 
Liquid  state,  hydrogenation  of  oils,  7. 
Liquids,  absorption  of  gases  by,  600. 
Liquefaction  apparatus,  462. 
Liquefaction  and  other  methods  for  the 

removal  of  carbon  monoxide,  460. 
Liquefaction  by  compression,  460. 
Liquefaction  of  water  gas,  594. 
Liquefaction,  partial,  468. 


INDEX 


743 


Lithium,  152. 

Lithium  phosphate,  155. 

Litigation,  81. 

Litigation  patent,  605. 

Liveing,  233. 

Liver  oil,  292. 

Lloyd,  308. 

Loew  process,  419. 

Long,  246. 

Loock,  329. 

Low,  430. 

Low-grade  fats  for  edible  purposes,  328. 

Low  titre  of  stearine,  380. 

Lowe  hydrogen  process,  484. 

Lowenstein,  317,  354. 

L'Oxhydrique  Frangaise,  560. 

Lubeck,  148. 

Lubricants,  358,  396,  411. 

Lubricants  containing  hardened  oil,  402. 

Lucas,  151,  194,  426. 

Ludwig,  327. 

Luening,  550. 

Luksck,  377. 

Lumbard,  405. 

Lysalbinate,  sodium,  207,  258. 

Lysalbinic  acid,  sodium  salts  of,  245. 

McBain,  272. 

McCarty,  85,  562. 

McCaw,  634,  671,  677. 

McCaw  Mfg.  Co.,  674. 

McCourt,  480. 

McElroy,  75,  149. 

McFarland,  691. 

Machine  tallow,  acid  free,  358. 

Machined  .soap  base,  370. 

Madinaveitia,  250. 

Magnesia,  150,  195,  428,  457,  480,  500, 

501. 

Magnesia-nickel,  476. 
Magnesium,  151,  246,  248,  267,  273. 
Magnesium  carbonate,  243. 
Magnesium  hydrate,  153. 
Magnesium  nitrate,  169. 
Magnesium  oxide,  119,  152,  254. 
Magnesium-platinum,  273. 
Magnesium  silicate,  187. 
Magnesium  sulphate,  140. 
Magnetic  catalyzer,  70,  169,  227. 
Magnetic  field,  Walter's,  70. 


Magnetic  filtration,  169. 
Magnetic  method  of  separation,  201. 
Magnetic  properties  of  carbonyl,  233. 
Magnetic  rotation  of  nickel  carbonyl, 

233. 

Magnetite,  499. 
Magnier,  3. 

Mailhe,  5,  24,  109,  256,  427. 
Majert,  52Q. 
Majima,  285. 
Maleic  acid,  280. 
Malonates,  48. 
Malt  extract,  107. 
Maltodextrin,  107. 
Manganese,    151,    168,    198,   455,   499, 

502. 

Manganese  carbonate,  151. 
Manganese  dioxide,  422,  502,  535. 
Manganese  ores,  495. 
Manganese  oxide,  152, 167,  402,  448,  457, 

501. 

Manganese  oxide  as  catalyzer,  21. 
Manganite,  calcium,  21. 
Manganosilicon,  524,  533. 
Manganous  oxide,  535. 
Mann,  438. 

Mannich,  259,  309,  315. 
Mannino,  85. 
Manufacture  of  catalyzers  on  the  large 

scale,  144. 
Manufacturing  cost  of  lard  substitute, 

322. 

Marbled  soap,  375. 

Marcusson,  25,  283,  302,  308,  310,  311. 
Marengo,  516. 
Margarine,  354,  399,  660. 
Margarine  and  lard  compound,  cotton- 
seed oil  in,  354. 
Margarine,  demand  for,  352. 
Margarine,  feeding  tests  on,  337. 
Margarine,  fish  oil  in,  339. 
Margarine  industry,  detriment  to,  329. 
Margarine  manufacture,  edible  fats  in, 

339, 
Margarine  manufacture,  introduction  of 

hydrogenated  products  in,  355. 
Margarine,  melting  point  of,  325. 
Margarine,  peanut  oil  for,  324. 
Margarine,  peanut  oil  in,  353. 
Margarine  plants,  329. 


744 


INDEX 


Margarines,  capacity  for  holding  water, 

355. 
Margarines   having  nutritive   value   of 

butter,  355. 
Marie,  275. 

Marine  animal  oils,  372. 
Marine  animal  oils,  specific  reaction  of, 

300. 

Marine  oils  and  rape  oil,  313. 
Marine  oils,  detection  of,  311. 
Marine  oils,  hydrogenated,  309. 
Markel,  38. 

Marsh  apparatus,  235. 
Martha,  230. 
Martin,  278. 
Maryott,  67. 

Maschinenbau-Anstalt  Humboldt,  465. 
Matte,  nickel,  232. 
Matte,  nickel  copper,  236. 
Maumene  number,  101. 
Mauricheau-Beaupre  method,  525. 
Mauricheau-Beaupre  system,  595. 
Maxted,  95,  166,  458,  509. 
May,  649. 

Mayer,  6,  123,  271,  283,  338,  339. 
Meal,  fish,  350. 

Mean  effective  temperature,  39. 
Measurements  of  resistance,  203. 
Mechanism  of  hydrogen  addition,  265. 
Meerschaum,  254,  259. 
Meigen,  9,  124,  128,  183,  210,  211,  215, 

220,  226,  313. 
Mellersch- Jackson,  197. 
Melting  point,   103,  202,  205,  281,  292, 

295,  298,  304,  310,  357,  362,  381,  392, 

410,  632,  633,  663,  695,  701. 
Melting-point  of  butter,  fat  having,  332. 
Melting  point  of  Burchanal's  product, 

345. 

Melting  point  of  cotton  oil,  341. 
Melting  point  of  margarine,  325. 
Mendelstam,  64. 

Menhaden  oil,  162,  298,  299,  353. 
Menhaden  oil,  composition  of,  300. 
Mercuric  chloride,  247,  525. 
Mercuric  oxide,  525. 
Mercury,  164,  437,  526. 
Mercury  chlorate,  273. 
Mercury  chloride,  144. 
Mercury  lamp,  73. 


Mercury  oxide,  264. 

Mercury  vapor  lamp,  33. 

Merz,  446. 

Mesaconic  acid,  280. 

Messerschmitt,  490. 

Messerschmitt  process  and  improved 
types  of  apparatus,  502. 

Messerschmitt  process,  reactions  in,  493,. 
494. 

Metal  catalyst,  traces  of,  356. 

Metal,  catalytic  in  oil,  319. 

Metal  hydrides,  275. 

Metal  oxide,  finely  divided,  348. 

Metal  oxides,  free  of  water,  223. 

Metal  powder,  catalyzer,  147. 

Metal  powders,  conductivity  of,  202, 

Metal  soap,  129,  198. 

Metal  soaps  as  catalyzers,  40. 

Metallic  diaphragm,  561. 

Metallic  diaphragm  cell,  550. 

Metallic  formates,  78,  191. 

Metallic  iron,  496. 

Metallic  mirror,  162,  235. 

Metallic  nickel,  124,  125,  183,  204,  210r 
213,  224,  225,  231,  236,  325. 

Metallic  nickel,  absence  of,  211. 

Metallic  nickel,  formation  of,  200. 

Metallic  nickel  in  catalyzers,  9. 

Metallic  nickel,  loss  of  conductivity,  219. 

Metallic  nickel  not  conveyor  of  hydro- 
gen, 220. 

Metallic  nickel,  precipitation  of,  137. 

Metallic  nickel  vs.  nickel  oxide,  207. 

Metallic  oleates,  191. 

Metallic  organosols,  253. 

Metallic  oxide  catalyzer,  19. 

Metallic  oxides,  107,  199,  203. 

Metallic  platinum,  245. 

Metallic  septa,  561. 

Metallic  soaps,  196. 

Metallic  zinc,  248. 

Metalloids,  254. 

Metallo-organic  compounds,  188,  197. 

Metallo-organic  salts,  47. 

Metals,  activity  of,  275. 

Metals  as  carriers,  254. 

Metals,  platinum,  242,  243. 

Methane,  110,  112,  260,  436,  453,  454, 
480,  494. 

Methane  as  an  impurity,  502. 


INDEX 


745 


Methane,  decomposition  of,  478. 

Methane,  manufacture  of,  529. 

Method,  digitonin,  283. 

Methods  of  hydrogenation,  1. 

Methylamine,  8. 

Methyl  ester  of  cinnamic  acid,  86. 

Methyl  oleate,  90. 

Methylcyclopentane,  257. 

Metropolitan  laboratories,  45. 

Metz,  276. 

Mewes,  470. 

Mexican  oil,  433. 

Meyer,  246,  253,  260,  310. 

Meyerheim,  25,  108,  283,  310,  328. 

Mica,  201,  251,  256. 

Mice,  experiments  with,  339. 

Mice,  tests  with,  357. 

Military  purposes,  hydrogen  for,  80. 

Milled  soap  from  hardened  oil,  formula 

for  making,  370. 
Miller,  584. 
Millian  test,  355. 
Milk,  332. 
Milk  of  lime,  468. 
Mineral  acids,  443. 
Mineral  oil,  21,  107,  403,  411. 
Mineral  oil  exposed  to  ultraviolet  rays, 

425. 

Mineral  oil  on  electrolyte,  561. 
Mineral  oils  and  residues,  421. 
Mineral  wool,  251. 
Mirror,  nickel,  125,  139,  205,  230. 
Mirror  test,  217. 
Mirrors,  metallic,  162. 
Mittasch,  155,  190,  256,  259,  260,    456 

479. 

Mixed  glycerides,  337. 
Mock,  107. 
Moeller,  423. 
Moellon,  407. 

Moissan,  114,  611,  613,  614,  615,  620. 
Moisture  content  of  margarine,  355. 
Moisture  forming  fatty  acid,  140. 
Moisture  in  hydrogen,  596.  v 

Moisture,  removal  of,  140. 
Moldenhauser,  447,  449,  499. 
Molten  lead,  267. 

Molten  metal,  hydrogen  from,  501. 
Molybdates,  152. 
Molybdenum,  168. 


Mond,   110,  229,  231,    232,    233,    236, 

448. 

Mond  and  Langer,  111. 
Mond  plant,  241. 
Monoxide,   carbon,  110,  166,  231,  237, 

240,  241,  250,  274. 
Monoxide,  silicon,  149. 
Monteux,  486. 
Montlaur,  251. 
Moore,  64,  96,  119,  123,  124,  166,  203, 

208,  317,  418,  448,  639,  693. 
Moore  process,  64,  639,  644,  693. 
Morawitz,  256,  260. 
Moreschi,  310. 
Morey,  157,  158,  159. 
Morgan-Brown,  85. 
Moritz,  559. 
Morrell,  90. 
Morrill,  87. 
Morris-Airey,  246. 
Morrison,  188,  635,  647,  653,  671,  689, 

697. 

Motor  spirit,  421. 
Motor  spirit  from  peat  tar,  422. 
Motor  spirit,  manufacture  of,  428. 
Mourew,  611,  613. 
Mouries,  329. 
Mueller,  588. 
Muller,  114,  137,  208,  289,  291,  326,  339, 

379,  449. 

Muller  speisefettfabrik,  A.  G.,  185. 
Multiple  Retort    System  of   Improved 

Equipment  Co.,  512. 
Multiple  type  of  electrolyzer,  572. 
Munroe,  252. 
Mustard  oil,  255. 
Mutton  tallow,  289,  657. 
Myristic  acid,  299,  300,  314. 

Naamlooze  Vennootschap,  7,  132. 
Naamlooze  Vennootschap  Ant.  Jurgens,. 

170,  212,  250,  348,  406. 
Naher,  449,  504. 
Naphtha,  424. 
Naphtha  acids,  83. 
Naphtha,  crude,  430. 
Nahptha  heptanophthene,  258. 
Naphthalene,  398. 
Naphthenes,  611. 
Naphthenic  acids,  crude,  402. 


746 


INDEX 


Naphthol,  222. 

Nascent  hydrogen,  271,  273,  274. 

Nascent  hydrogen,  reduction  of  oleic 
acid  by,  2. 

Nascent  nickel,  239. 

Nasini,  233. 

National  Ox-hydric  Co.,  570. 

National  Provisioner,  326. 

Natrolite,  261. 

Natural  gas,  420. 

Natural  gas,  decomposition  of,  478. 

Natural  gas,  hydrogen  from,  438,  484. 

Natural  Science  Society  in  Freiburg-in- 
Breisgau,  211. 

Neidenfuhr,  257. 

Netting,  iron,  58. 

Netting  of  nickel,  58. 

Netting,  silver,  58. 

Neumann,  256. 

Neutral  fats,  making,  32. 

Neutral  soap,  370. 

Neutralization  value,  288. 

Neville,  605,  621. 

New  York  Oxygen  Co.,  446. 

Ney,  66. 

Nickel,  17,  24,  39,  40,  54,  63,  69,  73,  74, 
95,  96,  108,  110,  112,  113,  119,  136, 
152,  158,  168,  175,  178,  179,  190,  198, 
208,  246,  265,  275,  276,  285,  289,  402, 
404,  406,  420,  423,  424,  426,  428,  429, 
430,  433,  437,  438,  449,  451,  455,  479, 
502,  513,  529,  531,  605,  609,  611,  613, 
618,  621,  628. 

Nickel,  absorption  of  hydrogen  by,  60. 

Nickel  acetate,  130,  138,  139,  147,  151, 
179,  183,  194,  198,  437. 

Nickel,  activation  of,  128. 

Nickel,  activity  of,  270. 

Nickel  adsorption,  174. 

Nickel-alumina,  176,  192. 

Nickel  ammonium  formate,  154. 

Nickel  and  cobalt,  separation  of,  170. 

Nickel  and  copper  carbonates,  55. 

Nickel  and  copper  catalyzer,  56. 

Nickel  and  copper  hydrates,  55. 

Nickel  and  glass,  176. 

Nickel  and  hydrogen  on  hydrocarbons, 
267. 

Nickel  and  nickel  carbonate,  225. 

Nickel,  anhydrous  oxides,  115. 


Nickel  arc,  174. 

Nickel-asbestos,  420, 

Nickel  benzoate,  186. 

Nickel  black,  210. 

Nickel,  blank  test,  306. 

Nickel  borate,  179,  183,  207. 

Nickel  borate  used  for  hardening,  anal- 
ysis of,  180. 

Nickel  boride,  186. 

Nickel  by  reduction  of  chloride,  271. 

Nickel  carbide,  120,  138,  186,  222. 

Nickel  carbonate,  41,  52,  54,  56,  58,  120, 
138,  142,  147,  148,  155,  159,  163,  165, 
169,  177,  186,  187,  190,  193,  197,  200, 
202,  205,  207,  219,  222,  223,  316,  437, 
451,  613,  617,  620. 

Nickel  carbonate,  ammoniacal,  154. 

Nickel  carbonate,  basic,  98,  225. 

Nickel  carbonate,  heating  in  oil,  227. 

Nickel  carbonyl,  20,  41,  43,  63,  119,  135, 
141,  177,  198,  210,  229,  233,  235,  239, 
443,  456,  480. 

Nickel  carbonyl  apparatus,  234. 

Nickel  carbonyl  as  a  source  of  nickel 
catalyzer,  237. 

Nickel  carbonyl,  decomposing  in  oil,  238 

Nickel  carbonyl,  decomposition  of,  20. 

Nickel  carbonyl,  decomposition  under 
pressure,  237. 

Nickel  carbonyl,  detonation  of,  231. 

Nickel  carbonyl  for  production  of  cata- 
lytic material,  43. 

Nickel  carbonyl  formation,  206. 

Nickel  carbonyl  non-conducting,  233. 

Nickel  carbonyl  plant,  241. 

Nickel  carbonyl,  preservation  of,  232. 

Nickel  carbonyl  process,  207. 

Nickel  carbonyl  process,  commercial, 
241. 

Nickel  carbonyl  reaction,  214,  217,  227. 

Nickel  carbonyl,  reactions  of,  231. 

Nickel  carbonyl  reaction  on  catalyzers, 
205. 

Nickel  carbonyl,  solubility  in  alcohol, 
235. 

Nickel  carbonyl,  solubility  in  chloro- 
form, 235. 

Nickel  carbonyl,  solubility  in  petroleum, 
235. 

Nickel  carbonyl  test,  184. 


INDEX 


747 


Nickel  carbonyl  test  for  metallic  nickel, 
204. 

Nickel  carbonyl  vapor,  234,  237. 

Nickel  carbonyl,  vapor  tension  of,  230. 

Nickel  carbonyl  volatilizer,  236. 

Nickel  catalysis,  270. 

Nickel  catalyst,  process  of  making,  159. 

Nickel,  catalytic  activity  of,  137. 

Nickel  catalyzer,  12,  98,  118,  284,  311, 
313,  324,  325,  357,  361,  392. 

Nickel  catalyzer  from  carbonyl,  237. 

Nickel  catalyzer  in  flaky  form,  140. 

Nickel  catalyzer,  making,  610. 

Nickel  catalyzer  with  silica,  175. 

Nickel-charcoal,  136. 

Nickel-charcoal,  activated,  150. 

Nickel-charcoal  catalyzer,  149. 

Nickel  chloride,  131,  166,  179,  328. 

Nickel  coating,  174. 

Nickel-cobalt  catalyzer,  128. 

Nickel,  colloidal,  160,  189,  207,  217,  417, 
437. 

Nickel,  comparison  of  activity,  187. 

Nickel  compounds,  conductivity  of,  202. 

Nickel  compounds,  existence  of  volatile, 
229. 

Nickel  compounds  in  catalytic  processes, 
147. 

Nickel  compounds,  reduction  of,  134. 

Nickel,  conductivity  of,  119. 

Nickel  content,  123. 

Nickel  content  in  hardened  oil,  324. 

Nickel  content  of  edible  fats,  326. 

Nickel  content  of  hardened  oil,  deter- 
mination of,  304 . 

Nickel  content  of  recovered  catalyst,  214. 

Nickel  content  on  a  daily  consumption 
of  hardened  fat,  326. 

Nickel-copper,  136. 

Nickel-copper  catalyzer,  128. 

Nickel  copper  matte,  Canadian,  236. 

Nickel,  decomposing  action  of,  268. 

Nickel,  degree  of  combination  with  hy- 
drogen, 271. 

Nickel,  deposition  of,  174. 

Nickel,  detection  in  hydrogenated  oil, 
339. 

Nickel,  detection  of,  89. 

Nickel,  determination  of,  203. 

Nickel  discs,  429. 


Nickel  dust,  81. 
Nickel,  effect  of,  210. 
Nickel,  effect  of  hot  fats,  325. 
Nickel,  electrical  disintegration,  142. 
Nickel,  electrically  disintegrated,  174. 
Nickel  electrode,  5,  539,  560,  571,  572, 

583. 

Nickel,  electrolysis  of,  175. 
Nickel,  excretion  of,  330. 
Nickel  exposed  to  nitrogen,  315. 
Nickel,  extraction  from  ores,  234. 
Nickel,  extraction  of,  237. 
Nickel,  fatty  acid  salts,  193. 
Nickel  filings,  613. 

Nickel,  finely  divided,  233,  248,  331,  344. 
Nickel,  first  use  as  a  contact  body,  110. 
Nickel  flake,  219. 
Nickel  for  making  hydrogen,  453. 
Nickel  for  removal  of  sulphur,  597. 
Nickel  formate,  48,  52,  79,  125,  130,  138, 

140,  147,  179,  183,  191,  192,  194,  198, 

200,  202,  205,  224,  225,  227,  406,  437. 
Nickel  formate,  basic,  226. 
Nickel  formate,  heating  in  oil,  227. 
Nickel  formate,  making,  224. 
Nickel,  formation  of,  219. 
Nickel,  free,  201. 
Nickel,  free  metal  necessary,  211. 
Nickel  from  nickel  carbonyl,  237. 
Nickel  gauze,  449. 
Nickel  gauze  cathode,  280. 
Nickel  glycerate,  197. 
Nickel,  "healthy,"  271. 
Nickel  hydrate,  109,  115,  131,  138,  146, 

147,  149,  153,  155,  159,  163,  169,  172, 

177,  186,  207,  210,  613,  615. 
Nickel  hydrate,  green,  232. 
Nickel  hydride,  66,  693. 
Nickel-hydrogen  system,  272. 
Nickel,  hydrogenation  with,  271. 
Nickel  hydroxide,  88,  158,  176,  202,  451. 
Nickel  in  candle  stock,  381. 
Nickel  in  cotton  oil,  328. 
Nickel  in  edible  products,  study  of,  326. 
Nickel  in  fats,  detection  of,  305. 
Nickel  in  fats,  determination  of,  328. 
Nickel  in  fish  oil,  338. 
Nickel  in  foodstuffs,  327. 
Nickel  in  hardened  fat,  347. 
Nickel  in  hardened  oils,  361. 


748 


INDEX 


Nickel  in  making  hydrogen,  448. 

Nickel  in  oil,  effect  of  hydrogen,  305. 

Nickel  in  oil,  test  for,  288,  292,  295,  296. 

Nickel  industry,  241. 

Nickel-iron,  136. 

Nickel,  Kerr  test  for,  296. 

Nickel  kettle,  use  of,  327. 

Nickel  kieselguhr,  672,  673. 

Nickel  kieselguhr  catalyzer,  206,  241. 

Nickel  leaves,  95. 

Nickel-lined  receptacles,  326. 

Nickel  linoleate,  130,  138. 

Nickel-magnesia,  456,  476. 

Nickel,  making  reduced,  171. 

Nickel,  metallic,  124,  125,  183,  188,  200, 
204,  207,  210,  213,  224,  231,  232,  236, 
325. 

Nickel,  metallic  condition  of  catalyzer, 
130. 

Nickel,  metallic,  tests  of,  214. 

Nickel  mirror,  125,  139,  205,  217,  230. 

Nickel,  nascent,  239. 

Nickel  netting,  52,  58. 

Nickel  nitrate,  55,  56,  58,  80,  109,  112, 
121,  126,  128,  131,  146,  150,  153,  155, 
169,  170,  172,  176,  197,  198,  199,  224, 
271,  412,  434,  437,  453,  456,  480,  613, 
620. 

Nickel  nitrate  and  sugar,  213. 

Nickel,  non-pyrophoric,  158,  276. 

Nickel  oleate,  130, 138, 183, 195,  219,  227. 

Nickel  oleate  in  hydrogenating  oils,  197. 

Nickel  on  copper,  167. 

Nickel  on  earthenware,  11. 

Nickel  on  glass,  119. 

Nickel  on  kieselguhr,  49. 

Nickel  on  pumice,  80. 

Nickel  ores,  232.  240. 

Nickel,  organic  salts  of,  47, 122, 135, 130. 

Nickel  oxalate,  148,  153,  194. 

Nickel,  oxidation  of,  413. 

Nickel  oxide,  19,  39,  40,  52,  54,  74,  88, 
108,  111,  114,  116,  118,  123,  135,  146, 
147,  151,  155,  162,  164,  168,  169,  186, 
189,  201,  202,  203,  204,  206,  207,  209, 
210,  213,  217,  221,  223,  262,  271,  325, 
396,  402,  406,  410,  419,  421,  426,  428, 
437,  451,  476,  479,  596,  611,  617. 

Nickel  oxide  and  aldehydes,  205. 

Nickel  oxide,  anhydrous,  220. 


Nickel  oxide  as  a  catalyzer,  224. 
Nickel  oxide  catalyzer,   120,   133,   199, 

218,  271,  313. 
Nickel  oxide  catalyzer  at  high  pressures, 

209. 

Nickel  oxide,  colloidal,  222. 
Nickel  oxide,  complex,  142. 
Nickel  oxide,  conductivity  of,  201. 
Nickel  oxide  flocculated,  218. 
Nickel  oxide  free  of  carbon,  222. 
Nickel  oxide  from  various  sources,  620. 
Nickel  oxide,  green,  98,  205. 
Nickel  oxide  in  a  dry  atmosphere,  reduc- 
tion of,  221. 
Nickel  oxide  catalysts,  measurements  of 

resistance  used,  216. 
Nickel   oxide  obtained  by   calcination, 

115. 

Nickel  oxide,  once  used,  207. 
Nickel  oxide  paste,  50. 
Nickel    oxide,     reduction    in    non-oily 

bodies,  220. 

Nickel  oxide,  reduction  of,  126. 
Nickel  oxide  suspended  hi  oil,  reduction 

of,  221. 

Nickel  oxide  tests,  201. 
Nickel  oxide  vs.  nickel,  128. 
Nickel  oxide,  voluminous,  224. 
Nickel  oxyhydrates,  220. 
Nickel  palmitate,  120. 
Nickel  pellets,  236. 
Nickel  perhydride,  270. 
Nickel  plates,  436. 
Nickel,  plating  with  carbonyl,  233. 
Nickel,  poisoned,  160,  270. 
Nickel  poisoning,  347. 
Nickel  poisons,  109. 
Nickel  potassium  cyanide,  124. 
Nickel  powder,  131,  148,  169,  330,  622. 
Nickel  protoxide,  617. 
Nickel,  pure,  128. 
Nickel,  pyrophoric  72,  110,  114,  115,  132,. 

422,  437,  613,  626. 

Nickel,  quantitative  determination,  328. 
Nickel,  reduced,  267. 
Nickel  reduction,  112. 
Nickel  reduction  in  ammonia,  171. 
Nickel,  removal  of,  94. 
Nickel,  reviving  for  carbonyl,  232. 
Nickel  rods,  21,  428. 


INDEX 


749 


Nickel  salt  catalyzer,  340. 

Nickel  salts,  200. 

Nickel  salts  of  organic  acids,  119. 

Nickel  "shapes,"  167. 

Nickel-silica,  175,  177,  192. 

Nickel  silicate,  160,  177,  185. 

Nickel  sludge,  142. 

Nickel  soaps,  94,  120,  122,  129,  139,  195, 

227,  288,  324,  325,  637,  656,  703. 
Nickel  soaps,  presence  of,  372. 
Nickel  solutions,  reduction  of,  170. 
Nickel  speiss,  232. 
Nickel,  spent,  recovery  of,  171. 
Nickel,  spongy,  280. 
Nickel  stearate,  120,  183,  227. 
Nickel  suboxide,  9,  118,  119,  122,  124, 

126,  138,  148,  182,  189,  200,  203,  207, 

208,  209,  426. 

Nickel  suboxide,  addition  compound,  221. 
Nickel  suboxide,  colloidal,  120. 
Nickel  suboxide,  existence  of,  210. 
Nickel  suboxide,  formation  of,  184 
Nickel  suboxide,  hydride,  216. 
Nickel  suboxide,  proof  of,  184. 
Nickel  sulphate,  109,  131,  133,  4£&,  137, 

155,  159,  177,  185,  273,  412,  610,  617, 

620,  627,  703. 

Nickel,  sulphide  in  soap,  372. 
Nickel  tartrate,  194. 
Nickel,  temperature  of  reduction,  114. 
Nickel,  toxicity  of,  326. 
Nickel,  traces  in  fat,  411. 
Nickel,  traces  of,  379. 
Nickel  tubes,  81,  529. 
Nickel  utensils,  use  of,  348. 
Nickel  vs.  nickel  oxide,  128. 
Nickel  wire,  52,  57,  81,  95. 
Nickel  wire  netting,  154,  156. 
Nickelized  asbestos,  12. 
Nickelized  pumice,  13,  50. 
Nickelware  in  the  preparation  of  food,  348. 
Nicolet,  176. 
Niobium,  254. 
Niobium  oxide,  152. 
Nitrate,  cobalt,  146. 
Nitrate,  copper,  55,  56,  146. 
Nitrate,  iron,  146. 
Nitrate,  metallic,  175. 
Nitrate,  nickel,  55,  56,  58,  109,  112,  121, 

126,  128,  131,  146,  150,  153,  199. 


Nitrate,  potassium,  274. 

Nitrate,  silver,  147. 

Nitrate,  sodium,  166. 

Nitrate,  thorium,  264. 

Nitrates  of  platinum  and  palladium,  249. 

Nitric  oxide,  251. 

Nitrils,  160. 

Nitrobenzene,  86,  107,  153,  248,  614. 

Nitro  compounds,  168,  195,  270. 

Nitrogen,  169,  171,  194,  442,  470. 

Nitrogen  and  hydrogen  mixtures,  532. 

Nitrogen,  boiling  point,  461. 

Nitrogen  Co.,  501. 

Nitrogen  Ges.  m.b.H.,  168. 

Nitrogen  oxides,  610. 

Nitrogen,  removal  of,  467,  597. 

Nitrogen,  treating  nickel,  315. 

Nitrogenous  colloid,  171. 

Nitromethane,  8. 

Nitrophenol,  8. 

Nitroprusside  test,  318. 

Noding,  505. 

Noll,  94. 

Non-pyrophoric  catalyzer,  276,  316. 

Non-pyrophoric  nickel,  626. 

Nood,  11. 

Normann,  7,  81,  183,  184,  200,  201,  203, 
204,  205,  206,  207,  211,  212,  223,  258, 
281,  284,  286,  313,  326,  327,  381,  405, 
614,  621,  629,  643,  655,  665,  682,  693, 
697. 

Normann  patent,  605,  703. 

Normann  patent  sale,  8. 

Normann  process,  9,  283,  614. 

Norwegian  hydrogenated  whale  oil, 
361. 

Nozzles,  injector,  72. 

Number,  acetyl,  284. 

Nut  margarine,  melting  point  of,  356. 

Obach,  547. 

Occluded  hydrogen,  132. 

Occlusion  of  hydrogen,  265. 

Octane,  86,  436. 

Octene,  86. 

Octodecyl  alcohol,  284,  311. 

Odor-forming  nitrogenous  impurities  in 

fish  oil,  360. 
Odor  from  gasoline  by  desulphurization, 

425. 


750 


INDEX 


Odor  not  absorbed  by  hardened  oil,  338. 

Odor  of  cracked  oils,  423. 

Odor  of  fish  oil,  338,  353,  360. 

Odor  of  soaps,  368. 

Odor  of  soaps  made  from  hardened  oils, 

372. 
Odor  of  soaps  made  from  hydrogenated 

oil,  377. 

Odor  of  talgol,  364,  368. 
Odorless  fish  oil,  362. 
Oechelhauser,  476. 
Oehme,  323. 

Oelverwertung,  G.  m.b.H.,  175. 
Oelwerke '  Germania,  9,  201,   207,  351, 

363,  399,  629. 
Oelwerke  hydrogen,  406. 
Oerlikon,  575. 
Oettle,  500. 
Offal,  fish,  350. 
Offerdahl,  330. 
Ohmann,  591. 
Oils,  albumin  in,  109. 
Oil,  almond,  301,  310,  658. 
Oil,  animal,  372. 
Oil,  artificial  geranium,  376. 
Oil  atomization,  342. 
Oil,  before  and  after  hardening,  89. 
Oil,  bleaching,  61. 
Oil,  blue  chamomile,  256. 
Oil,  calamary,  392. 
Oil  causes,  shortening,  345. 
Oil,  castor,  39,   88,   188,  242,  244,  248, 

250,  259,  275,  283,  284,  309,  313,  337, 

348,  359,  375,  381,  389,  394,  398,  409, 

659. 

Oil,  Chinese  wood,  361,  396,  400,  411. 
Oil,  chrysalis,  311,  361,  402. 
Oil,  cocoanut,  88,  282,  290,  309,  319,  331, 

333,  335,  355,  359,  364,  365,  366,  368, 

369,  370,  373,  375,  393,  398,  409,  439, 

692. 

Oil,  cod,  162,  301. 

Oil,  cold  liver,  242,  275,  310,  348,  637. 
Oil  colloids,  252. 
Oil,  color  test,  285,  301. 
Oil  containing  dissolved  nickel,  effect  of 

hydrogen  on,  306. 
Oil,  copra,  354,  361. 
Oil,  corn,  87,  96,  282,  334,  335,  343,  350, 

396,  408,  410,  439. 


Oil,  cotton,  20,  39,  48,  55,  56,  58,  60,  89,. 
96,  98,  104,  123,  128,  130,  134,  137, 
138,  140,  143,  148,  155,  161,  164,  177,. 
179,  181,  185,  194,  200,  201?  205,  213, 
214,  215,  216,  217,  218,  223,  225,  238, 
242,  248,  255,  263,  281,  282,  283,  285, 
289,  290,  291,  301,  304,  305,  306,  308, 
319,  320,  323,  325,  328,  331,  334,  336, 
338,  339,  341,  343,  344,  345,  346,  347, 
348,  349,  352,  354,  357,  361,  368,  383, 
396,  399,  407,  409,  410,  609,  610,  637, 
639,  645,  655,  660,  671,  675,  692,  697,. 
701,  703. 

Oil,  cracking,  150. 

Oil,  croton,  637,  658,  660,  661. 

Oil,  cruciferous,  316. 

Oil,  dab,  392. 

Oil,  decomposition  for  hydrogen,  473. 

Oil,  dogfish,  163. 

Oildom,  420. 

Oil,  edible,  338. 

Oil,  edible  hydrogenated,  319. 

Oil,  effect  of  impurities,  168. 

Oil,  electrical  treatment  of,  61. 

Oil,  essential,  hydrogen  number  of,  255. 

Oil,  filtration  of,  189. 

Oil,  fish,  25,  73,  83,  87,  147,  153,  155,. 
242,  248,  281,  285,  286,  287,  291,  292, 
295,  301,  328,  329,  338,  339,  349,  350, 
353,  358,  359,  360,  362,  368,  372,  378, 
390,  392,  394,  395,  396,  398,  101,  405,. 
409,  411,  607,  609,  612. 

Oil  for  cooking  purposes,  354. 

Oil  gas,  420,  595. 

Oil,  glycerine  in,  313. 

Oil,  grape  seed,  39. 

Oil,  hardened  and  flour,  646. 

Oil,  hardened,  expansion  of,  361. 

Oil  hardening  tank  explosion,  603. 

Oil,  herring,  163,  392. 

Oil,  hydrogen  absorbed,  695. 

Oil,  hydrogenated  and  baking  powder,, 
343. 

Oil,  hydrogenated,  harmless,  339. 

Oil,  impurities  affecting  catalyzer,  311. 

Oil  in  gas  cylinders,  592. 

Oil,  Japanese  wood,  275. 

Oil,  Java  citronella,  376. 

Oil,  kaya,  336. 

Oil,  keeping  qualities  of,  411. 


INDEX 


751 


Oil,  keeping  qualities  of  hydrogenated, 
337. 

Oil,  linseed,  12,  39,  89,  105,  122,  139,  154, 
155,  156,  181,  200,  201,  205,  213,  215, 
216,  217,  218,  223,  224,  225,  242,  275, 
282,  283,  301,  310,  352,  355,  359,  361, 
387,  393,  396,  398,  401,  406,  409,  607, 
609,  615,  657,  658. 

Oil,  liver,  292. 

Oil,  low  grade,  328. 

Oil,  magnetic  filtration  of,  169. 

Oil,  marine  animal,  300,  372. 

Oil,  menhaden,  162,  298,  299,  353. 

Oil,  mineral,  21. 

Oil,  mustard,  255. 

Oil  of  bitter  almonds,  367. 

Oil  of  citronella,  367. 

Oil  of  lavender,  367. 

Oil,  olive,  89,  96,  153,  167,  200,  203,  242, 
244,  253,  254,  287,  310,  315,  350,  410, 
439,  607,  609,  655,  656,  659,  660,  692. 

Oil,  olive,  substitute,  308*. 

Oil,  ozonized,  282. 

Oil,  Paint  and  Drug  Reporter,  390,  399. 

Oil,  palm,  44,  282,  336,  359,  361,  386, 
409. 

Oil,  Palma  Rosa,  376. 

Oil,  palm  kernel,  294,  309,  328,  331,  365, 
368,  374,  378,  385,  388,  393,  409. 

Oil,  partially  hydrogenated,  308. 

Oil,  peanut,  89,  96,  140,  250,  259,  282, 
286,  290,  291,  294,  304,  305,  310,  325, 
339,  347,  353,  355,  361,  369,  388,  393, 
396,  409,  692. 

Oil,  petroleum,  20,  154. 

Oil,  polymerized,  164. 

Oil,  poppy,  310. 

Oil,  rancid,  43. 

Oil,  rape,  39,  181,  223,  225,  285,  286,  301, 
309,  313,  315,  396,  609. 

Oil,  reduction  of  catalyzer  in,  140. 

Oil,  refining  chrysalis,  311. 

Oil,  remedial  food,  330. 

Oil,  ricinoleic,  301. 

Oil,  salad,  354. 

Oil,  sardine,  285,  353,  392,  411. 

Oil,  seal,  292,  330,  353. 

Oil,  semi-hardened,  161. 

Oil,  sesame,  155,  200,  204,  206,  209,  210, 
223,  225,  282,  285,  290,  291,  294,  304, 


305,  309,  310,  324,  325,  339,  347,  349 
637,  660,  692. 

Oil,  shark  liver,  391. 

Oil,  soluble,  280,  401. 

Oil,  soya  bean,  88,  92,  105,  155,  181,  210, 
282,  308,  333,  352,  353,  361,  409,  411. 

Oil  spray,  644. 

Oil  spray  process,  663. 

Oil,  steaming,  200. 

Oil,  sulphonated,  401,  407. 

Oil,  sunflower,  105,  297,  339,  361,  657. 

Oil  tar,  carbonyl  in,  233. 

Oil,  temperature  required  for,  218. 

Oil,  thickening  of,  61. 

Oil  to  be  hardened  for  edible  purposes, 
328. 

Oil,  torpedo  liver,  391. 

Oil,  train,  73,  373,  381. 

Oil,  treatment  with  copper  hydrate,  162. 

Oil,  treatment  with  silver  oxide,  162. 

Oil,  turkey  red,  280. 

Oil,  turtle,  392. 

Oil,  tung,  361,  396,  400,  411. 

Oil,  vacuum  treatment  of,  200. 

Oil,  vegetable,  319,  333. 

Oil,  whale,  30,  39,  55,  72,  89,  92, 155, 181, 
200,  205,  282,  284,  290,  291,  292,  295, 
301,  303,  314,  324,  325,  329,  330,  337, 
339,  352,  353,  355,  356,  360,  362,  368, 
378,  390,  392,  394,  395,  396,  397,  398, 
'  405,  409,  411,  609,  612. 

Oil,  wild  cucumber,  357. 

Oil,  wood,  242,  361,  396,  400,  411. 

Oil,  worsted,  308. 

Ointment,  410. 

Ointment,  palladium,  253. 

Okada,  285. 

Oleate,  125,  410. 

Oleate,  amyl,  91. 

Oleate,  benzyl,  91. 

Oleate,  butyl,  90. 

Oleate,  ethyl,  90. 

Oleate,  glycerine,  91. 

Oleate,  lead,  164. 

Oleate,  metallic,  196. 

Oleate,  methyl,  90. 

Oleate,  nickel,  130,  138,  183,  195,  227> 
219. 

Oleate,  palladious,  253. 

Oleate,  potassium,  253. 


752 


INDEX 


Oleate,  propyl,  90. 

Oleate,  sodium,  5,  263,  314. 

Olefine  bodies,  hydrogenation  of,  247. 

Olefines,  270,  423,  424. 

Oleic  acid,  12,  27,  29,  50,  62,  79,  128,  147, 

184,  215,  239,  242,  244,  248,  250,  275, 

280,  289,  297,  301,  314,  325,  326,  340, 

398,  439,  609,  617,  622,  623,  655. 
Oleic  acid  and  aniline,  91. 
Oleic  acid  and  hydrogen,  combination  of, 

439. 

Oleic  acid,  attempts    to  hydrogenate,  1. 
Oleic  acid,  chemically  pure,  218. 
Oleic  acid  equilibrium,  223. 
Oleic  acid,  hardening  of,  80. 
Oleic  acid,  hydrogenating  in  presence  of 

alkali,  79. 

Oleic  acid,  Merck,  214. 
Oleic  acid,  reduction  by  means  of  hy- 

driodic  acid,  2. 

Oleic  acid,  sulphonation  of,  5. 
Oleic  acid  vapor,  26. 
Oleic  amides,  84. 
Olein,  97,  337,  345,  373,  398,  440,  652, 

653,  654,  693,  694,  701,  706. 
Olein  soap,  377. 
Oleodipalmitin,  337. 
Oleo-distearine,  322. 
Oleomargarine;   see  also  Margarine. 
Oleomargarine     compositions,     use     of 

hardened  oil  in,  333. 
Oleomargarine,  hardened  fish  oil  in,  339. 
Oleomargarine,  utility  of  hydrogenated 

oils  in,  356. 
Oleo-oil,  355. 

Oleo  stearine,  323,  341,  646,  647,  677. 
Oleo-stearine  compound,  321. 
Oleo-stearine,  cost  of,  319. 
Oleo-stearine,  substitute  for,  358. 
Oleostearopalmitin,  323. 
Oleo  stock,  354. 
Olinit,  403. 
Olive  oil,  89,  96,  153,  167,  200,  203,  205, 

244,  253,  254,  287,  310,  315,  350,  410, 

439,    607,    609,    655,    656,    659,    660, 

692. 

Olive  oil,  hydrogenated,  242. 
Olive  oil  substitute,  308. 
Ore,  spathic  iron,  454. 
Ores,  nickel,  232,  240. 


Ores  of  manganese  in  place  of  iron  ore, 
495. 

Ores,  sulphide,  511. 

Organic  compounds,  catalytic  hydrogen- 
ation of,  187. 

Organic  compounds  of  metals,  130. 

Organic  metal  salts  as  catalyzer,  47. 

Organic  salts  of  metals,  188. 

Organic  nickel  salts,  125. 

Organic  salts,  nickel  oxide  from,  138. 

Organic  salts  of  nickel,  122, 138, 191,  200. 

Organo-metallic  compound  of  nickel,  232. 

Organo-metallic  compounds,  231. 

Organosol  as  catalyst,  167. 

Organosol,  osmium,  261. 

Organosol,  palladium,  254. 

Organosols  in  hydrogenating,  257. 

Organosols  of  palladious  hydroxide,  253. 

Organosols  of  palladium,  253. 

Organosols  of  palladium  oleate,  253. 

Organosols  of  platinous  hydroxide,  253. 

Organosols  of  platinum,  253. 

Osann,  273. 

Oscillatory  discharge,  435. 

Osmate,  261. 

Osmate,  alkali,  254,  259. 

Osmate,  sodium,  262. 

Osmium,  254,  258,  261,  275,  600. 

Osmium  black,  250. 

Osmium,  colloidal,  261. 

Osmium,  colloidal  hydroxides  of,  258. 

Osmium  dioxide,  249,  262. 

Osmium  organosol,  261. 

Osmium  tetraoxide,  125,  249,  258,  261. 

Osmium  zeolite,  261. 

Ostromisslenski,  424. 

Oswald,  159. 

Overhardening,  219. 

Overheating  of  oil,  372. 

Oxalate,  48. 

Oxalate  cobalt,  426. 

Oxalate  chromium,  426. 

Oxalate,  ferrous,  151. 

Oxalate,  iron,  426,  502. 

Oxalate,  nickel,  148,  153,  426,  194. 

Oxide,  nitric,  251. 

Oxalate,  platinous,  243. 

Oxalate,  platinum,  249. 

Oxhydrogenators,  559. 

Oxidation  of  ammonia,  catalyzer  for,  256. 


INDEX 


753 


Oxide,  aluminum,  119. 

Oxide  and  organic  salt  catalyzers,  125 

Oxide,  arsenic,  164. 

Oxide,  carbonic,  230,  234,  237. 

Oxide  catalyzer,  19,  133. 

Oxide,  cerium,  119. 

Oxide,  cobalt,  88,  112,  146,  199,  262. 

Oxide,  copper,  116,  135,  146. 

Oxide,  green  nickel,  98. 

Oxide,  iron,  199. 

Oxide  lanthanum,  119. 

Oxide,  lead,  162. 

Oxide,  magnesium,  119,  254. 

Oxide,  nickel,  19,  39,  40,  52,  54,  74,  88, 
108,  111,  116,  118,  120,  123>  135,  146, 
147,  164,  186,  189,  199,  202,  203,  204, 
206,  207,  209,  213,  217,  218,  223,  262, 
271,  325. 

Oxide  of  cerium  catalyzer,  21. 

Oxide  of  iron  catalyzer,  21. 

Oxide  of  manganese  catalyzer,  21. 

Oxide,  osmium,  125. 

Oxide,  silver,  54,  119. 

Oxide,  thorium,  264. 

Oxide,  tin,  262. 

Oxide,  titanium,  119,  348. 

Oxide,  zinc,  262,  515. 

Oxide,  zirconium,  119,  251. 

Oxides,  metallic,  107,  199,  203. 

Oxides,  nitrogen,  610. 

Oxides  of  pyrophoric  nickel,  115. 

Oxidizable  components  of  fats,  350. 

Oxidizing  catalyst,  259. 

Oxy-acetylene  welding,  584. 

Oxychloride,  carbon,  230. 

Oxygen,  274,  610. 

Oxygen,  activation  of  catalyzer  by,  260. 

Oxygen,  addition  to  fatty  oil,  282. 

Oxygen,  as  catalyzer  poison,  250. 

Oxygen  by  arc  decomposition,  558. 

Oxygen  by  electrolysis  of  water,  536. 

Oxygen  containing  hydrogen,  601. 

Oxygen,  effect  on  platinum,  264. 

Oxy-fatty  acids,  638. 

Oxygen  in  hydrogen,  596. 

Oxygen,  manufacture  of,  536. 

Oxygen,  removal  of,  597,  600. 

Oxygen,  sale  of,  595. 

Oxygen,  standards,  603. 

Oxyhydrates,  nickel,  220. 


Oxystearic  acid,  79,  439. 
Oyobigawa,  532. 
Ozone,  273. 
Ozonized  oils,  282. 

Paal,  6,  100,  242,  246,  248,  249,  250,  252, 

255,  264,  270,  306,  323,  400,  406,  637, 

638,  665,  697,  703. 
Padgett,  6,  116,  267,  402,  423. 
Paint,  flatting,  409. 
Palladinized  calcium  carbonate,  316. 
.Palladious  chloride,  247,  252,  253. 
Palladious  hydroxide,  organosols  of,  253. 
Palladium,  8,  17,  29,  39,  54,  55,  57,  62, 

63,  67,  68,  69,  96,  108,  133,  137,  147, 

166,  167,  173,  178,  179,  187,  250,  262, 

265,  268,  275,  289,  390,  404,  406,  415, 

428,  433,  449,  531,  600. 
Palladium-ammonium  chloride,  263. 
Palladium,  amorphous,  272. 
Palladium  black,  5,  11,  41,  222,  242,  251, 

276. 

Palladium  catalyzer,  14,  100,  242,  315. 
Palladium-charcoal  catalyzer,  309. 
Palladium  chloride,  55,  63,  79,  100,  140, 

221,  242,  246,  256,  270. 
Palladium  coke  catalyzer,  62. 
Palladium,  colloidal,  255,  306,  659. 
Palladium,  cost  of,  255,  256. 
Palladium,  crystalline,  272. 
Palladium,  effect  of  potassium  cyanide, 

161. 

Palladium-gold,  277. 
Palladium  hydride,  269. 
Palladium  hydrosol,  264. 
Palladium  hydroxide,  262. 
Palladium,  loss  of,  256. 
Palladium  oleate,  organosols  of,  253. 
Palladium  on  metal-oxides,  14. 
Palladium  organosols,  253. 
Palladium,  pressure  of  hydrogen  on,  277. 
Palladium  protochloride,  242. 
Palladium,  pyrophoric,  268. 
Palladium-silver,  277. 
Palladium  sol,  279. 
Palladium  solutions,  221. 
Palladium  sponge,  277. 
Palladium,  spongy,  268. 
Palladium  supported  on  various  bodies, 

248. 


754 


INDEX 


Palladium  wire,  57. 

Fallacious  chloride,  255. 

Palma  Rosa  oil,  376. 

Palmitate,  nickel,  120. 

Palmitic  acid,  3,  83,  298,  299,  300,  314, 
326,  345,  378,  379,  655. 

Palmitin,  377,  439. 

Palmitodistearine,  318. 

Palm  kernel  oil,  294,  309,  328,  331,  365, 
368,  374,  378,  385,  388,  393,  409. 

Palm  nut  oil,  88. 

Palm  oil,  44,  282,  336,  359,  361,  386,  409. 

Paper,  rosin  for,  403. 

Paraffin,  59,  220,  423. 

Paraffin  hydrocarbons,  250. 

Paraffin  oil,  430. 

Paraffin  wax,  12,  148,  198,  222. 

Paranitraniline,  86. 

Parker,  33. 

Partial  hydrogenation,  96,  317,  346. 

Partial  reduction  of  nickel  oxide  or  hy- 
drate, 210. 

Partial  saturation  of  glycerides,  322. 

Partially  hydrogenated  oils,  308. 

Partially  hydrogenized  oil,  634. 

Passive  palladium,  268. 

Passivity  of  metals,  276. 

Passivity  of  nickel  as  a  catalyzer,  116. 

Passmore,  300,  613,  624,  629. 

Patent  leather,  406. 

Patent  litigation,  605,  630. 

Payet,  148. 

Peanut  oil,  89,  96,  140,  250,  259,  282, 
286,  290,  291,  294,  304,  305,  310,  324, 
325,  347,  353,  355,  361,  369,  388,  393, 
396,  409,  692, 

Peanut  oil,  edible,  339. 

Peanut-margarine,  294. 

Peanut-oleo,  294. 

Pekelharing,  339. 

Pellischek,  294. 

Pennie,  630,  649. 

Pentadecane,  436. 

Pentamethylene  hydrocarbons,  257. 

Pentane,  116. 

Peptonizing  milk,  356. 

Percentage  of  catalyzer,  99,  102. 

Percentage  of  cotton  oil,  320. 

Percentage  of  nickel,  17. 

Perchlorate,  potassium,  273. 


Perfume  composition  for  soaps,  377. 

Perfume,  soap,  364,  376. 

Perhydride,  nickel,  270,  271. 

Perkin,  233. 

Perl,  251. 

Permutit,  173,  261. 

Peroxides,  422. 

Persulphates,  422. 

Peters,  8,  161. 

Petersen,  5,  275. 

Petroleum,  20,  530,  611. 

Petroleum,  absorption  of  hydrogen,  430, 

Petroleum  as  a  solvent,  96. 

Petroleum,  carbonyl  in,  233. 

Petroleum,  catalyzer  for,  151. 

Petroleum,  cracking  of,  420. 

Petroleum,  desulphurization,  11. 

Petroleum  distillates,  257. 

Petroleum  ether,  67. 

Petroleum,  for  making  hydrogen,  484. 

Petroleum  hydrogenation,  154. 

Petroleum,  hydrogenation  of,  418. 

Petroleum  oil  for  reduction,  198. 

Petroleum  oil  subjected  to  electric  arc,. 

436. 

Pfeilring,  29. 
Pfeilring  reagent,  388. 
Pharmaceutical  fats,  411. 
Phenanthrene,  220. 
Phenol,  86,  113,  116,  153. 
Phenomena  of  catalytic  poisons,  166. 
Phenyl  propiolate,  187. 
Phenylpropionic  acid,  86. 
Philipow,  6. 
Philipp,  519. 
Phillips,  20. 
Phorone,  270. 

Phosphate,  152,  162,  190,  525. 
Phosphate,  lithium,  155. 
Phosphate,  sodium,  343. 
Phosphide  of  hydrogen,  14. 
Phosphites,  174. 
Phosphoiybdic  acid,  214. 
Phosphomolybdic  acid,  184,  200. 
Phosphoretted  hydrogen,  231,  610. 
Phosphorus,  254,  443,  454,  455,  596,  610, 
Phosphorus  hydride,  598. 
Phosphorus,  red,   164. 
Phosphotungstic  acid,  214. 
Phthalic  anhydride,  264. 


INDEX 


755 


Physetoleic  acid,  291,  380. 

Physiological  action  of  hardened  oil,  324, 
339. 

Phytosterol,  283,  284,  289,  291,  294,  308, 
310,  311. 

Phytosterol  acetate,  309,  325. 

Pickard,  356. 

Pickering,  303. 

Picker  trough,  320. 

Picrate,  sodium,  250. 

Pictet,  72,  471. 

Pictet  oil  process,  478. 

Pier,  601. 

Pierron,  167. 

Pilat,  21. 

Pinene,  280. 

Pintsch,  510. 

Piperine,  270. 

Piperinic  acid,  270. 

Pitch,  431. 

Piva,  446. 

Planes,  limited,  420. 

Plaster  of  Paris,  450. 

Plasters,  410. 

Platinic  chloride,  252. 

Platinochloride,  copper,  243. 

Platinochloride-hydrochloric  acid,  253. 

Platinous  hydroxide,  221. 

Platinous  hydroxide,  organosols  of,  253. 

Platinous  oxalate,  243. 

Platinum,  34,  39,  54,  55,  58,  96,  112,  136, 
158,  166,  167,  178,  230,  248,  250,  259, 
262,  270,  275,  277,  280,  289,  297,  337, 
402,  422,  427,  433,  443,  513,  529,  531, 
605,  609,  611,  618,  621,  628. 

Platinum-alumina,  262. 

Platinum  and  carbon  catalyst,  259. 

Platinum  anode,  280. 

Platinum  black,  89,  242,  246,  264,  269, 
283,  619. 

Platinum  black  charcoal  catalyzer,  259. 

Platinum  catalyzer,  249,  283. 

Platinum  chloride,  147,  242,  260,  264. 

Platinum,  colloidal,  33,  245,  600. 

Platinum-copper,  260. 

Platinum,  effect  of  oxygen  on,  264. 

Platinum  electrode,  6,  274,  562. 

Platinum,  electrolytic,  257. 

Platinum  gauze,  449. 

Platinum  hydrochloride,  242. 


Platinum  hydrosols,  249. 

Platinum  hydroxide,  257. 

Platinum  metals,  243. 

Platinum  metals,  hydrogen  transfer,  269. 

Platinum  netting,  58. 

Platinum  on  charcoal,  catalyzer,  259. 

Platinum  organosols,  253. 

Platinum,  oxygenated,  264. 

Platinum  protochloride,  242. 
,  Platinum  salts  available  as  catalyzers, 
249. 

Platinum  sponge,  10,  619. 

Platinum  sulphate,  242. 

Platinum  tetrachloride,  256. 

Platinum  zeolite,  261. 

Pleiss,  563. 

Plumbite,  425. 

Pohlman,  435. 

Poison,  catalyzer,  14,  109,  112,  113,  118, 
153,  155,  160,  164,  166,  189,  198,  208, 
223,  243,  247,  250,  254,  255,  264,  270, 
419,  420,  442,  443,  453,  454,  485,  525, 
596,  610,  615,  618,  620. 

Poison,  nickel,   109. 

Poison,  removing  from  oil,  161. 

Poison  squads,  326,  361. 

Poisoned  nickel,  270. 

Poisoning  by  carbon  monoxide,  167. 

Poisoning  by  nickel,  347. 

Polarity  reversal,  585. 

Polarity  reversal,  prevention  of,  603. 

Polenske  method,  308. 

Polenske  value,  309. 

Polishing  compound,  411. 

Polymerization,  285. 

Polymerization  of  unsaturated  oils  by 
action  of  ultraviolet  light,  397. 

Polymerized  drying  oils,  87. 

Polymerized  hydrocarbon,  422. 

Polymerized  oil,   164. 

Polymerizing  and  hydrogenating  oil,  396. 

Pomilio,  279. 

Pompili,  546. 

Pontianak,  96. 

Pontianak  resin,  405. 

Poppy  oil,  310. 

Porcelain,  251,  256. 

Porcelain,  unglazed,  467. 

Forges,  421. 

Portable  hydrogen  plants,  595, 


756 


INDEX 


Porter,  251. 

Posen,  513. 

Potassium  aluminate,  154. 

Potassium  bromate,  274. 

Potassium  carbonate  electrolyte,  541, 
550. 

Potassium  chlorate,  273. 

Potassium  chloroplatinate,  243. 

Potassium  cyanide,  161,  165,  273. 

Potassium  nickel  cyanide,  208. 

Potassium  nitrate,  274. 

Potassium  oleate,  252,  253. 

Potassium  silicate,  256. 

Potassium  silicon1  uoride,  156. 

Potassium  thiocarbonate,  296. 

Poulenc  Freres,  357. 

Poulsen  arc,  246. 

Powder,  hydrogenated  oil  as  a,  342. 

Powder,  nickel,  330. 

Powder,  silver,  267. 

Powder,  soap,  368. 

Powdered  hydrogenated  oil,  411. 

Practice,  hydrogenation,  412. 

Prall,  288,  324. 

Frail's  modified  test  for  nickel,  305. 

Pratis,  516. 

Precautions  in  handling  hydrogen,  590. 

Precipitated  gold,  267. 

Precipitation  of  carbon,  method  of  pre- 
venting, 493. 

Preheated  hydrogen,  40. 

Preparation  of  catalysts,  methods  of, 
153. 

Preparation  of  nickel  carbonyl,  229. 

Prescher,  308. 

Preservation  of  nickel  carbonyl,  232. 

Pressing  edible  fats,  334. 

Pressure  apparatus,  600. 

Pressure  diminishing  defines,  423. 

Pressure,  effects  of,  85,  89,  97,  101,  168, 

.   209,  424. 

Pressure,  effect  on  reduction,  170. 

Pressure  on  carbonyl,  237. 

Pressure  tank  for  hydrogen,  594. 

Preston,  430. 

Prevention  of  hydrogen  explosions,  591. 

Process,  hardening,  610. 

Process  of  Sabatier  and  Senderens,  5. 

Processes  involving  application  of  elec- 
tricity, -3. 


Procter,  634. 

Proctor  &  Gamble,  first  experimental 
plant,  672. 

Proctor  &  Gamble  Co.,  16,  56,  350. 

Proctor  &  Gamble  Co.  vs.  Berlin  Mills 
Co.,  630. 

Producer  gas,  446,  449,  485. 

Production  of  neutral  hydrogenated  fats, 
32. 

Products  of  combustion  of  internal  com- 
bustion engines,  480. 

Products  of  hydrogenation,  105. 

Promoter,  152,  168,  190,  223,  254,  455. 

Propane,  438. 

Properties  and  uses  of  various  hardened 
oils,  352. 

Properties  of  nickel  carbonyl,  230. 

Properties  of  soaps  made  with  hardened 
oils,  30. 

Propiolate,  187. 

Propionates,  48. 

Propionic  acid,  280. 

Proportions  of  hardened  oil  in  soaps,  369. 

Propylene,  260. 

Propyloleate,  90. 

Protablinate,  sodium,  258. 

Protalbinic  acid,  255. 

Protalbinic  acid,  sodium  salts  of,  245. 

Protective  action  of  colloids,  257. 

Protective  colloid,  244,  255,  257. 

Protein,  118. 

Protoalbinate,  sodium,  207. 

Protochloride,  palladium,  242. 

Protochloride,  platinum,  242. 

Protohydroxide,  platinum,  242. 

Protoxide  of  nickel,  114. 

Pullman,  450. 

Pulverization  of  hardened  oil,  343. 

Pumice,  50,  69,  75,  80,  109,  110,  149, 168, 
171,  174,  176,  190,  192,  197,  254,  260, 
434,  453,  486,  501,  502,  607. 

Pumice,  nickelized,  13. 

Pumice,  platinized,  437. 

Pumping  hot  hydrogen  gas,  26. 

Pungs,  200,  201,  203,  204,  205,  206. 

Purger,  563. 

Purification  method  of  Bosch  &  Wild, 
598. 

Purification  of  gas,  595. 

Purification  of  hydrogen,  488,  595. 


INDEX 


757 


Purification  of  oils  by  copper  hydrate, 
162. 

Purifier  for  separating  dust  and  sulphur 
compounds,  599. 

Purifying  hydrogenated  fats,  350. 

Pyridine,  84. 

Pyrite  cinder  in  manufacture  of  hydro- 
gen, 510. 

Pyrites,  511. 

Pyrophoric  bodies,  614. 

Pyrophoric  catalyst,  protection  of,  159. v 

Pyrophoric  catalyzer,  159,  169,  171,  276. 

Pyrophoric  iron,  592,  615. 

Pyrophoric  metal,  624. 

Pyrophoric  nickel,  72,  110,  114,  115,  132, 
422,  437,  613,  615,  626. 

Pyrophoric  palladium,  268. 

Pyrrole,  264. 

Qualitative  test  of  conductivity,  202. 
Quantitative  analysis  of  used  catalyst, 

219. 
Quantitative    determination    of    nickel, 

328. 

Quartzite,  251. 

Quentin  &  Guillien  method,  532. 
Quincke,  229,  233. 
Quinine,  210. 
Quinine  hydrochloride,  187. 

Rabenalt,  596. 

Rack,  181,  184. 

Rakitin,  6. 

Ramage,  608,  612. 

Rancid  oils,  43. 

Rancid-tending  oxidized  products,  351. 

Range  of  temperature,  39. 

Rape  oil,  39,  181,  223,  225,  285,  286,  301, 

309,  313,  315,  396,  609. 
Rape  oil,  hardening  of,  225. 
Rape  oil  in  olive  oil,  determination  of, 

315. 

Rare  metals  as  catalyzers,  242. 
Rate  of  absorption  of  hydrogen,  71. 
Rather,  58. 
Rating,  tariff,  382. 
Rats,  experiments  with,  339. 
Rays,  chemically  active,  35,  36,  41. 
Rays,  solar,  501. 
Reaction,  carbonyl,  204. 


Reaction  of  steam  with  iron,  485. 

Reaction  of  Tortelli  &  Jaffe,  301. 

Reagent,  Tschugaeff,  327. 

Recipes  for  soap  stock,  366. 

Recovering  catalytic  material,  43. 

Recovering  spent  catalyzer,  188. 

Recovery  of  catalytic  material,  132. 

Recovery  of  catalyzer,  62,  170,  171. 

Recovery  of  flaky  catalyzer,  141. 

Recovery  of  spent  catalyzer,  179. 

Redgrove,  105,  534. 

Red  phosphorus,  164. 

Reduced  cobalt,  267. 

Reduced  copper,  267. 

Reduced  iron,  166,  267. 

Reduced  nickel,  267. 

Reducer,  413. 

Reducing  catalyzer,  156. 

Reducing  chamber,  145. 

Reducing  gases,  210. 

Reduction  apparatus,  Kayser's,  156. 

Reduction  by  metal  hydrides,  275. 

Reduction,  catalyzer,  611. 

Reduction,  coefficient  of,  126. 

Reduction,  electrolytic,  88,  279. 

Reduction  in  oil,  139,  140. 

Reduction  of  catalyzer,  113,  139. 

Reduction  of  catalyzer  in  various  sus- 
pensory bodies,  222. 

Reduction  of  nickel  compounds,  appa- 
ratus for,  134. 

Reduction  of  nickel  oxide,  126. 

Reduction  of  nickel  oxide  by  aldehydes, 
205. 

Reduction  of  nickel  oxide  with  hydrogen, 
210. 

Reduction  of  unsaturated  acids,  275. 

Reduction  temperature,  627. 

Refining  by  alkali,  162. 

Refining  chrysalis  oil,  311. 

Refining  hydrogenated  fats  to  produce 
edible  products,  351. 

Reformatoky,  8. 

Refraction,  index  of,  281,  282,  287,  292. 

Regeneration  of  a  spent  nickel  silicate 
catalyzer,  179. 

Regeneratibn  of  catalyzer,  428. 

Regeneration  of  nickel  catalysts,  171. 

Regeneration  of  spent, catalyzer,  241. 

Reichert-Meissl  number,  101,  295. 


768 


INDEX 


Reichert-Meissl  value,  309. 

Reid,  58,  76. 

Remedial  food,  oil  as,  330. 

Removal  of  moisture,  140. 

Removal  of  sulphur  from  petroleum,  11. 

Removing  catalyzer  poisons,  161. 

Removing  nickel,  94. 

Renard,  423,  596. 

Renard's  apparatus,  539. 

Renovated  butter,  329. 

Reoxidizing  catalyzer,  142. 

Replacement  of  carbon  monoxide  by 
hydrogen,  444. 

Resin,  96. 

Resin,  guayule,  405. 

Resin,  pontianak,  405. 

Resistance,  electric,  216. 

Resistance  of  nickel  oxide,  203. 

Retorts,  cast  iron,  613. 

Reuter  Process  Co.;  409. 

Reversal  of  polarity,  585,  603. 

Review  of  the  art,  1. 

Revivification  of  catalyzer,  105. 

Revivifying  metallic  catalysts,  188. 

Reychler,  2,  608,  612. 

Reynolds,  169. 

Rhead,  274. 

Rheinheimer,  304. 

Rhodes,  424. 

Rhodium,  250,  261,  275,  419,  449. 

Rhodizonic  acid,  salts  of,  231. 

Ribot,  374. 

Rice,  602. 

Richards,  536,  544. 

Richardson,  174,  195,  656,  687. 

Richter,  21,  96,  166,  317,  526,  640,  663, 
689. 

Ricinoleic  acid,  301,  280,  440,  609. 

Ricinolic  acid,  313,  439. 

Ridsdale,  95,  509. 

Riedel,  323. 

Rinati,  62. 

Rincker,  438,  473. 

Rincker  &  Wolter,  595. 

Rincker  &  Wolter  system,  473 

Rincker-Wolter  portable  hydrage  appa- 
ratus, 483. 

Rinoker-Wolter  process,  modified,  483. 

Rittman,  424,  437. 

Rivals,  104. 


Robson,  81,  106,  208. 

Rods  of  nickel,  21. 

Roentgen  rays,  61,  269. 

Rogers,  405. 

Rolla,  170. 

Rosauer,  3. 

Rose,  479. 

Rosemary  oil,  377. 

Rosin,  96,  297,  364,  371,  378,  385,  387, 

388,  393,  403. 
Rosin  soap,  393. 
Rostin,  434. 

Rotary  electrolyzer  of  Aigner,  558. 
Rotary  retort,  458. 
Roth,  6,  286,  309,  637,  658,  665,  697, 

703. 

Rowlands,  588. 
Ruggeri,  312. 
Ruthenate,  alkali,  254. 
Ruthenium,  250,  254,  261,  275. 
Ruthenium  chloride,  258. 
Ruthenium,  colloidal  hydroxides  of,  258. 
Ruthenium,  tetroxide,  258. 

Sabatier,  5,  11,  13,  29,  52,  58,  85,  112, 
113,  114,  126,  127,  132,  160,  175,  209, 
212,  220,  221,  256,  270,  271,  275,  405, 
427,  606,  611,  613,  615,  620,  657,  702. 

Sabatier  hydrogen  process,  529. 

Sabatier's  method,  213. 

Sachs,  7,  439,  595. 

Sadtler,  411. 

Safety  devices,  590. 

Safrol,  86. 

Salad  oil,  354. 

Salad  oil,  peanut  oil  as,  308. 

Salad  oil,  soya  bean  as,  353. 

Salammoniac  turpentine  soap,  384. 

Sale  of  hydrogenated  oil,  635. 

Salmon  oil,  411. 

Salt,  513. 

Salted  soap,  yield  of,  365. 

Sandarac,  96. 

Sandelin,  303. 

Sander,  446,  534. 

Sanders,  476. 

Saponification,  351,  375,  395. 

Saponification  number,  282,  292,  381. 

Saponification  of  hydrogenated  fats,  369. 

Saponification,  products  of,  379. 


INDEX 


759 


Saponification  value,  101,  304,  309,  310, 

314,  379. 

Saponifying  for  fatty  acids,  378. 
Saponin,  389. 
Saponin  powder,  389. 
Sardine  oil,  105,  353,  392,  411. 
Sardine  oil,  Japanese,  285. 
Sassafras  oil,  377. 
Saturated  hydroxy  fatty  acids,  39. 
Saubermann,  502. 
Sauer,  447. 
Sawdust,  109,  208. 
Sayre,  350,  410. 
Saytzeff,  5. 

Schaal,  363,  366,  374,  376,  398. 
Schaefer  producer,  506. 
Schall,  365. 
Scherieble,  44. 
Schering,  421. 
Schicht,  89,  105,  361. 
Schicht,  A.  G.  and  Grim,  89,  106. 
Schick,  184,  251,  258. 
Schiller,  11. 
Schilling,  308. 
Schlinck  &  Co.,  21. 
Schmidt,  3,  107,  276. 
Schmidt  electrolyzer,  575. 
Schmidt  multiple  cell,  541. 
Schmitz,  402. 

Schneider,  155,  190,  256,  260,  456,  479. 
Schoenfeld,  179,  181,  183,  184,  305. 
Scholl,  532. 
Schonthan,  29. 
Schoop,  591. 
Schoop  system,  543. 
Schrapinger,  400. 
Schrauth,  88,  400,  409. 
Schroeder,  121. 
Schuck,  373,  393. 
Schuckert  plant,  557. 
Schuckert  system,  551. 
Schut,  339. 
Schwarcman,  95,  171. 
Schwarcman's  method,  262. 
Schwartz,  520. 
Schweitzer,  80,  349. 
Schwerin,  262. 
Schwoerer,  12,  682. 
Scientific  American,  426 
Seal  oil,  292,  330,  363,  411. 


Sears,  702. 

Sebille,  589. 

Secondary  reactions,  exclusion  of,  218. 

Sectional  type  electrolyzer,  575,  577. 

Seeker,  112,  534. 

Seidenberg,  297. 

Seifenseider  Zeitung,  249. 

Selective  hydrogenation,  25,  97. 

Selenates,  152. 

Selenite,  ammonium,  155. 

Selenites,  152. 

Selenium,  254. 

Selenium  compounds,  113. 

Semi-boiled  soaps,  369. 

Semi-carbazone,  270. 

Semi-reduced   hydrogenation   catalyzer, 

209. 

Semi-solid  fat,  632. 
Senderens,  5,  7,  11,  13,  58,  85,  112,  113, 

114,  209,  212,  220,  275,  405,  606,  611, 

657,  702. 

Separation  of  nickel  from  cobalt,  235. 
Sesame  margarine,  294. 
Sesame  oil,  155,  200,  204,  206,  209,  210, 

223,  225,  282,  285,  290,  291,  294,  304, 

305,  309,  310,  324,  325,  339,  347,  349, 

637,  660,  692. 
Sesame-oleo,  294. 
Sesquioxide,  precipitated,  262. 
Shale,  hydrogen  from,  473. 
Shale  oil,  430. 
Shark  liver  oil,  391. 
Shark  oil,  411. 

Shaving  soap,  cold  process,  368. 
Shaving  soaps,  hardened  oil  in,  376. 
Shaw,  26,  106,  588. 
Shellac,  96. 

Shipment  of  catalytic  material,  160. 
Shortening  agent,  340,  357. 
Shortening  agent,  vegetole  as  a,  357. 
Shortening  and  leavening  composition  of 

hydrogenated  oil,  343. 
Shortening  composition,  modification  of, 

342. 

Shortening  effect  of  hard  fat,  341. 
Shortening  for  cooking,  354. 
Shortening  materials,  646. 
Shortening  values,  691. 
Shriver  apparatus,  675. 
Shriver  filter  press,  417. 


760 


INDEX 


Shriver  oxy-hydrogen  generator,  541, 
542. 

Schuck,  87. 

Shukoff,  20,  41. 

Shukoff 's  nickel  earbonyl  process,  207. 

"Sical,"  419. 

Siedler,  261,  457. 

Siegmund,  105,  211,  223,  226,  227. 

Siemens,  550,  600. 

Siemens  Bros.  &  Co.,  547. 

Siemens  &  Obach  cell,  547. 

Siemens  &  Schuckert  Co.,  523. 

Sieverts,  265,  276,  277. 

Silent  electric  discharge,  33,  73. 

Silex,  417. 

Silica,  133,  167,  173,  175,  178,  254,  454, 
455. 

Silica,  non-abrasive,  179. 

Silicate,  alkaline,  150. 

Silicate,  aluminum  and  magnesium,  187. 

Silicate,  nickel,  160,  177,  185. 

Silicate  of  soda,  169. 

Silicate,  potassium,  256. 

Silicate,  sodium,  530. 

Silicates,  168. 

Silicic  acid,  174,  189,  262. 

Silicide,  aluminum,  520. 

Silicides  for  generation  of  hydrogen,  519. 

Silicious  material,  149.  4 

Silicofluoride,  156. 

Silicol,  533. 

Silicol  process,  523. 

Silicon,  178,  522,  530. 

Silicon  and  caustic  soda,  reaction  be- 
tween, 523. 

Silicon  hydrate,  192. 

Silicon  hydride,  removal  of,  598. 

Silicon  hydrogen  process,  523. 

Silicon  monoxide,  149. 

Silicon  tetrafluoride,  175. 

Silicospiegel,  524. 

Silk,  56. 

Silver,  54,  55,  246,  265,  276,  422,  428. 

Silver  bromide,  273. 

Silver  chloride,  273. 

Silver  iodide,  273. 

Silver-iron  couple,  459. 

Silver  netting,  58.. 

Silver  nitrate,  147,  169. 

Silver  oxide,  54,  55,  119,  162. 


Silver-palladium,  277. 

Silver  powder,  267. 

Silver  sol,  262. 

Silver  wire,  267. 

Simplex  Refining  Co.,  434. 

Siveke,  7,  123,  135,  207,  212,  351,  372. 

Size  of  apparatus  in  hardening,  100. 

Sjoquist,  105. 

Skita,  242,  244,  245,  250,  255,  256,  260, 

270,  400. 
Sludge  acid,  83. 
Sludge,  nickel,  142. 
Sludges,  waste  liquor,  531. 
Sluggishness  of  catalyzers,  24. 
Smoking  point,  692. 

Smoking  point  of.hydrogenated  fats,  338. 
Smith,  278. 

Snelling,  191,  192,  419. 
Snelling  diffusion  process,  531. 
Snelling  hydrogen  method,  484. 
Soap,  30,  88,  129,  252,  600,  633. 
Soap  base  for  toilet  soaps,  369. 
Soap,  color  of,  381. 
Soap,  chrysalis  oil  in,  311. 
Soap,  darkening  of,  372. 
Soap,  demand  for,  352.  . 
Soap,  Eschweger,  374. 
Soap  filling,  375. 

Soap,  fish  oils  in  manufacture  of,  353. 
Soap  formula,  367. 
Soap  from  fatty  acids,  408,  409. 
Soap  from  hardened  linseed  oil  and  rosin, 

387. 

Soap  Gazette  and  Perfumer,  119. 
Soap  in  electrolyte,  552. 
Soap,  iron,  129. 
Soap  making,  fish,  oil  in,  360. 
Soap-making  materials,  358. 
Soap-making  purposes,  whale  oil  for,  330. 
Soap  making,  revolution  in,  612. 
Soap  making,  utilization  of  hydrogen- 

ated  oils  in,  358. 
Soap,  metal,  129,  195. 
Soap,  nickel,  ,94,  120,  122,  129,  139,  195, 

227,  324,  325,  372,  637,  656. 
Soap  perfumes,  364,  376. 
Soap  powder,  368. 
Soap,  rosin  in,  403.     - 
Soap  stock,  690. 
Soap  stock  containing  krutolin,  383. 


INDEX 


761 


Soap  stock,  recipes  for,  366. 

Soap,  wax,  129. 

Soap  with  polymerized  oil,  397. 

Soc.    de   stearinerie   et   Savonnerie   de 

Lyon  and  Berthon,  198. 
Soc.  Industrielle  de  Products  Chimiques, 

171,  189. 

Soc.  L'Air  Liquide,  599. 
Soc.  L'Hydrogene,  511. 
Soc.  L'Oxylithe,  169. 
Soc.  Lyonnaise,  438. 
Soda-lime,  446,  478,  520. 
Sodium,  425. 
Sodium  aluminate,  176. 
Sodium  aluminate-silicate,  173. 
Sodium  aluminum  silicate,  256. 
Sodium  aluminum  silicide,  519. 
Sodium  amalgam,  208,  273. 
Sodium  bicarbonate,  520. 
Sodium  bisulphate,  517. 
Sodium  carbonate,  128. 
Sodium  chlorate,  273. 
Sodium    chloride,    164,    166,    223,    513, 

528. 

Sodium  cinnamate,  187. 
Sodium  for  making  hydrogen,  519. 
Sodium  hydrosulphite,  273. 
Sodium  hypophosphite,  137. 
Sodium  lysalbinate,  207,  258. 
Sodium  nitrate,  166. 
Sodium  nitroprusside,  318. 
Sodium  oleate,  5,  314. 
Sodium  permutite,  261. 
Sodium  phenyl  .propiolate,  187. 
Sodium  phosphate,  343. 
Sodium  picrate,  250. 
Sodium  protalbinate,  207,  258. 
Sodium  silicate,  169,  177,  179,  530. 
Sodium  silicofluoride,  156. 
Sodium  sulphate,  140,  163,  166,  189. 
Sodium  sulphide,  166,  189. 
Soft  soap,  384. 
Solar  rays,  501. 
Sole  leather,  407. 
Solidification  point,  210,  214,  215,  225, 

295,  298,  304,  665. 
Solidifying  point,  292. 
Solomonoff,  83. 
Soltsien  test,  309. 
Soluble  oil,  280,  401. 


Solubility  of  gases  in  copper,  278. 
Solubility  of  hydrogen  and  nitrogen  in 

iron,  279. 

Solubility  of  hydrogen  in  metals,  266. 
Solubility  of  soaps,  371. 
Solvents,  96,  404. 
Solvents,  hydrogenation  in.  280. 
Solvents,  hydrogenating  with,  67. 
Solvents,  use  of,  310. 
"Sorption,"  272,  274. 
Soxhlet  extraction  thimble,  214. 
Soya  bean  oil,  88,  92,  105,  155,  181,  210, 

282,  308,  352,  353,  361,  409,  411. 
Soya  bean  oil,  hydrogenated,  333. 
Spathic  iron  ore,  454.. 
Spathic  iron  ore,  use  of,  499. 
Specific  gravity,  281,  292,  295. 
Speed  of  reaction,  226. 
Speiss,  nickel,  232. 
Spent  catalyzer,  219,  227. 
Spent  catalyzer,  treatment  of,  170,  171. 
Spieler,  192. 

Spinacerie,  hydrogenation  of,  313. 
Spitzer  generator,  505. 
Splitting  fats,  398. 

Splitting  of  hydrogenated  fish  oil,  378.. 
Sponge,  56. 
Spongy  iron,  502,  505. 
Spongy  iron,  employment  of,  492. 
Spongy  nickel,  237. 
Spongy  palladium,  268. 
Spongy  platinum,  10. 
Spongy  Swedish  iron,  500. 
Spray  and  film  process,  15. 
Spray  or  films  of  oil,  12. 
Spraying  of  oil,  16. 
Spraying  process,  125,  663,  693. 
Sprinkmeyer,  309. 
Spueing>  405. 
Squalene,  313,  391. 
Stability  of  lard  compound,  322. 
Stabilizer,  color,  .336. 
Stahl,  278. 
Stahlschmidt,  274. 
Standard  Oil  Co.,  432. 
Starch,  122,200,452. 
Stark,  249. 
Starrels,  408. 
Stationary  catalyzjer,  22. 
Stationary  hydrogen  plants,  595. 


762 


INDEX 


Steam,  action  on  carbon  to  produce  hy- 
drogen, 527. 

Steam  and  aluminum  under  pressure, 
419. 

Steam  distillation  of  saturated  fatty 
acid,  14. 

Steam-iron  process,  695 

Steam  on  hydrocarbons,  21. 

Steam  through  molten  metal,  hydrogen 
by,  501. 

Steam,  use  of  superheated,  500. 

Steam  vacuum  deodorization,  319. 

Steam  with  oil  during  cracking,  429. 

Steaming  of  fat,  351. 

Stearate,  lead,  164. 

Stearate,  metallic,  196, 

Stearate,  nickel,  120,  183,  227. 

Stearic  acid,  12,  50,  83,  220,  223,  242, 
275,  280,  285,  289,  298,  300,  312,  314, 
325,  326,  340,  345,  360,  378,  379,  398, 
408,  622. 

Stearic  acid  by  chlorination,  2. 

Stearic  acid,  ethyl  ester  of,  51.    . 

Stearic  acid  in  reduction,  198. 

Stearic  glyceride,  292. 

Stearic  soap,  129. 

Stearine,  292,  326,  346,  354,  355,  399, 
407,  439,  651,  652,  653,  654,  693,  694, 
701,  706. 

Stearine  and  edible  fat  industry,  hard- 
ened oils  in,  373. 

Stearine,  artificial,  303. 

Stearine  candle,  378. 

Stearine  from  olein,  separation  of,  373. 

Stearine  industry,  373. 

Stearine,  low  titre  of,  380. 

Stearine,  percentage  of,  in  butter  substi- 
tutes, 346. 

Stearine,  removal  of  excess,  332. 

Stearine  soap,  377. 

Stearine  substitute,  84. 

Stearine,  synthetic,  884. 

Steel  alloys,  529. 

Steel  wool,  591. 

Steffan,  29. 

Stereo-chemistry  of  glycerides,  325. 

Sterol,  291. 

Sterol  content  of  hardened  fats,  283. 

Sterol-free  bodies,  284. 

Sterol,  separation  of,  283. 


Stern,  108. 

Stevens,  11,  400. 

Stirring  during  hydrogenation,  620,  626. 

Stokes  Co.,  F.  J.,  53. 

Strache,  425. 

Strache  hydrogen  system,  498. 

Stransky,  421,  425. 

Straub,  324. 

Strontia,  428. 

Strontium,  152. 

Strontium  nitrate,  155. 

Strontium  sulphate,  527. 

Stuart,  517. 

Stuart  scrap  iron  method,  517. 

Stucker,  424. 

Stuckert,  168. 

Stuffing  fat,  408. 

Submicrons,  218. 

Suboxide  hydride,  210. 

Suboxide,  nickel,  9,  122,   124,   126,   138, 

148,  182,  200,  203,  207,  208,  209,  406. 
Suboxide,  nickel,  proof  of,  184. 
Suboxide  of  nickel  catalyst,  210. 
Suboxides  of  metals,  211. 
Substitute,  butter,  684. 
Substitute  for  olive  oil,  308,  350. 
Substitutes,  lard,  701. 
Succinates,  48. 
Suchy,  530. 
Sudfeldt  Bros.,  30. 
Sugar,  121,  213,  224,  600. 
Sugar,  cane,  200. 
Sugita,  93. 

Suida,  211,  223,  226,  227. 
Sulphate,  162. 
Sulphate,  aluminum,  263. 
Sulphate,  calcium,  151. 
Sulphate,  copper,  273. 
Sulphate,  magnesium,  140. 
Sulphate,  nickel,  109,  131,  133,  135,  137, 

155,  273,  627. 
Sulphate  of  iron,  21. 

Sulphate  of  platinum  and  palladium,  249. 
Sulphate,  platinum,  242. 
Sulphate,  sodium,  140,  166,  189. 
Sulphates,  presence  in  catalyzer,  163. 
Sulphide,  hydrogen,  15,  163,  165,  166, 

208,  231,  443,  487. 
Sulphide  of  barium  process,  526. 
Sulphide  of  nickel  in  soaps,  372. 


INDEX 


763 


Sulphide  sodium,  166,  189. 

Sulphides,  treatment  with  steam,  511. 

Sulpho  acids,  79. 

Sulpho-iso-oleic  acid,  79. 

Sulphonated  oil,  401,  407. 

Sulphonation  of  oleic  acid,  5. 

Sulphonation  process,  5. 

Sulpho-oxystearic  acid,  79. 

Sulphur,  109,  112,  113,  118,  137,  153, 
155,  160,  164,  166,  232,  254,  421,  422, 
423,  442,  443,  451,  454,  596,  609,  627. 

Sulphur  chloride,  164,  422. 

Sulphur  compounds,  372,  419,  420. 

Sulphur  compounds  of  platinum,  256. 

Sulphur  dioxide,  166. 

Sulphur  dioxide,  removal  of,  698. 

Sulphur,  effect  on  iron,  485. 

Sulphur  from  gas,  removal  of,  597. 

Sulphur  in  cracking  oils,  use  of,  433. 

Sulphur  in  fats  and  oils,  detection  of,  318. 

Sulphur  in  hydrogen,  163. 

Sulphur,  removal  from  petroleum,  11. 

Sulphur  removal,  in  making  hydrogen, 
505. 

Sulphur,  removal  of,  597,  598,  599. 

Sulphuretted  hydrogen,  609,  618. 

Sulphuric  acid,  109,  223. 

Sulphuric  acid,  action  on  zinc,  515. 

Sulphuric  acid  and  iron,  595. 

Sulphuric  acid,  effect  of  carbonyl,  231. 

Sulphuric  acid  electrolyte,  544,  562. 

Sulphuric  acid  esters,  84. 

Sulphuric  acid  on  oleic  acid,  3. 

Sulphurous  acid,  487. 

Sulzberger,  160,  176,  178,  179,  263. 

Sunflower  oil,  105,  297,  339,  657. 

Sunflower  oil,  hardened,  361. 

Sunlight  soap  factory,  361. 

Superheated  steam  on  hydrocarbons,  21. 

Superhydrogenated  edible  product,  333. 

Surface  condensation,  274. 

Suspended  nickel,  traces  of,  324. 

Suzuki-Shoten  Co.,  208. 

Svendsen,  314. 

Swartley,  586. 

Swartley  separators,  583. 

Sweetmeat,  407. 

Swift  &  Co.,  636,  650,  651,  687. 

Synthesis  of  ammonia,  259. 

Synthetic  stearine,  334. 


Synthetic  triolein,  211,  214. 
System  of  automatic  control,  586. 
System  of  de  Kadt,  38. 

Table  fats,  649. 

Tailor's  chalk,  411. 

Talc,  411. 

Talgela,  363. 

Talgelin,  363. 

Talgin,  362. 

Talgit,  289,  291,  379,  403. 

Talgit,  a  marine  oil,  289 

Talgol,  283,  284,  287,  311,  361,  362,  363, 

364,  399. 

Talgol  and  candelite,  374. 
Talgol  and  cocoarmt  oil,  366. 
Talgol  as  a  substitute  for  tallow,  373. 
Talgol  in  grained  soap,  371. 
Talgol  in  shaving  soap,  376. 
Talgol  in  toilet  soaps,  365. 
Talgol  soap,  365. 
Tallow,  9,  289,  310,  329,  354,  355,  359, 

363,  364,  368,  374,  383,  394,  398,  409, 

439,  661. 

Tallow,  artificial,  303. 
Tallow,  beef,  309,  325. 
Tallow  in  lard,  method  of  detecting, 

308. 

Tallow-like  product,  656. 
Tallow  soaps,  372. 
Tamari,  151. 
Tanks  for  hydrogen,  594. 
Tanning  industry,  358,  405. 
Tantalum,  254,  256,  427. 
Tantalum  oxide,  152. 
Tar,  151,  431. 

Tar  and  mineral'Di!,  treatment  of,  438. 
Tar  oil,  430. 

Tar  oils,  carbonyl  in,  233. 
Tariff  commiaeion,  105. 
Tariff  rating  on  hardened  oil,  382. 
Tartaric  acid,  122,  200. 
Tartrate,  nickel,  194. 
Tartrates,  48. 

Tartrates  in  electrolyte,  562. 
Taylor,  647. 
Tchugaeff,  294. 
Techno-chemical  laboratories,   18,   120, 

134,  155,  605. 
Teissier,  534. 


764 


INDEX 


Tellurium,  254. 

Temperature,  effect  of,  85,  92,  97,  101, 
168. 

Temperature  of  hydrogenation,  39,  268, 
619. 

Temperature  of  reduction,  109,  112, 
114. 

Temperature  of  treatment  of  lard  com- 
pound, 319. 

Temperature,  reduction,  627. 

Temperature  required  for  different  oils, 
218. 

Tentative  standards  for  oxygen  and  hy- 
drogen, 603. 

Tessie  du  Motay,  444. 

Test,  bromination,  303. 

Test,  Halphen,  104,  317. 

Testelin,  423. 

Tests  of  catalyzer,  214. 

Tests  on  silicol  or  silicon  alloys,  530. 

Testrup,  16,  606,  616. 

Tetrachloride,  platinum,  256. 

Tetrahydronaphthalene,  268. 

Tetrahydrophenanthrene,  267. 

Tetroxide,  osmium,  249,  258. 

Tetroxide,  ruthenium,  258. 

Texas  solar  oil,  cracking  of,  425. 

Thallium,  265. 

Thallium  salts,  527. 

Thermal  considerations,  40. 

Thermal  decomposition  of  nickel  oleate, 
198. 

Thermolyzing,   175. 

Thesis  by  Agder  218. 

Thickening  oils,  61. 

Thickening  oils  and  fats,  process  for,  44. 

Thiele,  259,  280,  309,  316. 

Thieme,  197. 

Thiocarbonate,  potassium,  296. 

Thompson,  269,  326,  339,  352,  354,  360, 
437. 

Thoria,  348,  427. 

Thorium,  168,  256,  455. 

Thorium  nitrate,  455. 

Thorium  oxide,  264. 

Thron,  251. 

Thyme  oil,  377. 

Tin,  246,  254,  265. 

Tin  chloride,  164. 

Tin  oxide,  262,  448. 


Tin-zinc-aluminum  alloy,  525. 

Tinkler,  423. 

Tissier,  23. 

Titanates,  178. 

Titanic  acid,  262,  427. 

Titanium,  168,  256,  455,  499. 

Titanium  lactate,  154. 

Titanium  oxide,  119,  152,  348. 

Titanium  purifier,  600. 

Titanous  sulphate,  178. 

Titoff,  274. 

Titre,  103,  288,  317,  322,  333,  355,  379, 

395,  695. 

Toilet  soap,  hardened  fish  oil  in,  374. 
Tolhausen,  85. 
Tolmacz  &  Co.,  52. 

Toluene,  258,  426,  438.     See  also  Toluol, 
Toluol,  434.     See  also  Toluene. 
Tomassi,  273. 
Tommasini  cell,  560. 
Torpedo  liver  oil,  391. 
Tortelli,  300,  309,  312. 
Toxic  unsaturated  bodies,  323. 
Toxicity  of  traces  of  nickel,  326. 
Traces  of  suspended  nickel,  324. 
Triangular  charts,  644. 
Train  oil,  73,  295,  373,  381. 
Tran,.381. 
Transfer   of   hydrogen  by  gas  holders,, 

76. 

Transference  of  hydrogen,  271. 
Transparent  glycerine  soaps,  369,  375. 
Transportation  of  hydrogen,  533. 
Treatment  of  oil  with  metallic  catalyzer,, 

15. 

Tricaproin,  337. 
Tributyrin,  337. 
Trihydroxybenzene,  530. 
Trimethylamine,  84. 
Trinitrophenol  salts,  129. 
Triolein,  67,  85,  220,  322,  337. 
Triolein,  pure,  214. 
Triolein,  synthetic,  211,  218. 
Tripalmitin,  85. 
Triple  furnace  of  Bosch,  509, 
Tripler,  460. 

Tristearine,  85,  291,  318,,  337. 
Tristearirje,^  specific  gravity  of,  281. 
Troost,  270. 
Tschugaeff  s  reagent,  327. 


INDEX 


765 


Tsujimoto,  302,  311,  313,  360,  361,  391. 

Tubandt,  216. 

Tubular  cracking  apparatus,  422. 

Tully  process,  511. 

Tuna  fish  oil,  411. 

Tung  oil,  396,  400,  411. 

Tungstate,  barium,  155. 

Tungstates,  152. 

Tungsten,  106,  168,  499. 

Tungstic  acid,  262. 

Turbidity  test,  297. 

Turkey  red  oil,  84,  280. 

Turner,  11. 

Turpentine,  hydrogen  from,  473. 

Turpentine,  spirits  of,  231. 

Turtle  oil,  392. 

TwitcheU,  298,  300. 

Twitchell    process,    29,   370,   379,   394, 

408. 
TwitcheU  reagent,  388. 

Ubbelohde,  12,  131,  424. 

Ubbelohde  and  Goldschmidt,  1. 

Uchida,  107. 

Ueno,  104,  336,  392,  600. 

Uhlinger,  480. 

Ultraviolet  light,  62. 

Ultraviolet    light    on   catalytic   action, 

effect  of,  33. 
Ultraviolet  light,  polymerization  of  oils 

by,  397. 

Ultraviolet  rays  on  oil,  425. 
Undecoic  acid,  297. 
Undecylic  acid,  280. 
Underwriters'  Laboratories,  603. 
Unsaponifiable  constituents  of  hardened 
.'  oils,  283. 

Unsaponifiabl.e  bodies,  content  of,  283. 
Unsaponifiable   matter,   295,   310,   395, 

398. 

Unsaturated  acids,  275,  279. 
Unsaturated  bodies  in  fats,  333. 
Unsaturated  bodies,  toxic,  323. 
Unsaturated  compounds,  36. 
Unsaturated  constituents  of  petroleum, 

418. 

Unsaturated  fatty  acids,  285. 
Unsaturated  hydrocarbons,  250. 
Unsintered  nickel  powder,  169. 
Unstable  hydrides,  275., 


Uranates,  178. 
Uranium,  106,  168,  256,  455, 
Uranium  oxide,  152,  427. 
Urutol,  363. 
Used  catalyzer,  227. 
Used  catalyzer,  analysis  of,  219. 
Uses  of  hydrogenated  oils,  390. 
Uses  of  hydrogenated  oils  and  their  util- 
ization in  soap  making,  358. 
Utescher,  33,  40,  73. 
Utilization  of  fish  oil,  350. 
Uyeno,  525. 

Vacuum  deodorization,  26. 

Vacuum,  treatment  of  catalyzer,  139. 

Valerian  bodies,  332. 

Valeric  acid,  280. 

Valpy,  151,  194,  426. 

Vanadate,  calcium,  155. 

Vanadium,  168,  173,  455,  502. 

Vanadium  oxide,  152. 

Van  Arsdel,  96,  166,  317. 

Van  Leent,  89. 

Van  Scoyoc,  558. 

Vapor,  nickel  carbonyl,  234. 

Vareille  apparatus,  561. 

Varnish,  407. 

Varnish  gums,  405. 

Varrentrapp,  88. 

Varrentrapp  reaction,  3,  409. 

Vaseline,  198,  308. 

Vavon,  269. 

Vegetable  butter  composition,  332. 

Vegetable  oil,  319. 

Vegetable  oil,  hydrogenated,  333. 

Vegetable  stearine,  323. 

Vegetole,  357. 

Velocity  curves,  269. 

Vereingte  chemische  Werke,  63,  257. 

Vereingte  chemische  Werke  A.-G.,  14. 

Vereingte  Chem.  Works,  256. 

Verona-Rinati,  62,  259. 

Vieth,  330. 

Vigdorcik,  315,  316. 

Vignon,  454,  458,  467,  500. 

Vignon's  apparatus,  500. 

Viscosity,  295. 

Viscosity  of  dough,  342. 

Voit  laboratory,  324. 

Volatile  organic  acid,  use  of,  194. 


766 


INDEX 


Volatile  nickel  compound,  235. 
Volatilizer  for  carbonyl,  236. 
Voluminous  nickel  oxide,  213,  224. 
Von  Phul,  677,  697. 
Von  Schonthan,  29. 
Voswinckel,  52. 
Vuk,  348. 

Wachtolf,  473. 

Walker,  74,  107,  346,  639,  663,  689. 

Walrus  oil,  411, 

Walter,  34,  35,  70,  169,  441,  613. 

Wanz,  520. 

Ward  Co.,  636. 

Ward  Baking  Co.,  646. 

Ware,  nickel-lined,  326. 

Waser,  5. 

Waste  fats,  utilization  of,  349. 

Waste  liquor  sludges,  531. 

Water  content  of  kaolin,  275. 

Water,  effect  of,  223,  226. 

Water,  effect  on  catalyzer  reduction,  221. 

Water,  electrolysis  of,  536. 

Water  gas,  10,  163,  177,  210,  232,  237, 

241,  420,  433,  449,  460,  529,  595,  597, 

615,  619,  620. 
Water  gas  and  lime,  594. 
Water  gas  and  steam  in  presence  of 

nickel  or  iron,  448. 
Water  gas  as  a  source  of  hydrogen,  441, 

444. 

Water-glass,  169. 

Water  held  by  hardened  fats,  355. 
Water  in  hydrogen,  166. 
Water  in  oil,  295. 
Water  or  steam  with  oil  during  cracking, 

429. 

Water  purger,  563. 
Water  seal  explosion  arrester,  603. 
Water-soluble  protective  colloid,  245. 
Water  under  pressure,  effect  on  fatty 

acids,  89. 

Water  vapor  and  carbon  monoxide,  107. 
Wax  grain  soaps,  386. 
Wax,  paraffin,  12, 148, 186, 198,  220,  222. 
Wax  soaps,  129. 
Waxes,  83,  107. 
Waxes,  hydrogenation  of,  337. 
Weber,  368,  369,  377. 
Weineck,  3. 


Weith,  446. 

Welded  iron  electrolyzer,  554. 

Wells,  161,  164,  176,  422,  430. 

Wentzki,  596. 

Wesson,  172,  338. 

Weston,  302,  303. 

Whale  oil,  30,  39,  55,  72,  89,  92,  155, 181, 
200,  205,  282,  284,  287,  290,  291,  292, 
295,  301,  303,  314,  342,  325,  329,  330, 
337,  339,  352,  353,  355,  356,  360,  362, 
368,  378,  390,  332,  394,  395,  396,  397, 
398,  405,  409,  411,  609,  612. 

Whale  oil,  bacteria  free,  330. 

Whale  oil  in  soap,  30. 

Wheat  flour  with  comminuted  hardened 
oil,  340. 

Wheeler,  274. 

Whitaker,  94,  424,  430. 

White,  391,  421. 

White  color  of  hardened  vegetable  fats, 
340. 

White-grained  soap,  369,  372,  398. 

White  soft  soaps,  374. 

White  wax  grain  soaps,  386. 

Wieland,  222,  248,  269. 

Wielgolaski,  61. 

Wijs,  304. 

Wilbuschewitsch,  16,  18,  46,  105,  132, 
133,  337,  351. 

Wilbuschewitsch  process,  283. 

Wild,  451,  454,  598. 

Wilde,  2,  606. 

Wilhelmus,  388. 

Wilkinson,  11. 

Willstatter,  6,  264,  283,  310. 

Williams,  8,  12,  19,  122,  208,  209,  643. 

Wimmer,  47, 108,  126,  130, 140, 198,  406. 

Wimmer  and  Higgins,  110. 

Wimmer  and  Higgins  apparatus,  48. 

Windans,  283,  310. 

Windisch,  248,  249. 

Winkler,  418. 

Wintergreen  oil,  377. 

Wire  electrode,  581. 

Wire  gauze,  432. 

Wire-gauze,  safety  device,  590. 

Wire,  iron,  267. 

Wire  netting,  456. 

Wire,  nickel,  95. 

Wire,  silver,  267. 


INDEX 


767 


Wohler,  602. 

Wolfbauer,  294. 

Wolfbauer  method,  317,  355. 

Wolter,  473. 

Woltereck,  21,  423. 

Wood  charcoal,  136,  274. 

Wood  oil,  242,  275,  361,  396,  400,  411, 

Woodruff,  172. 

Wool,  56,  263,  171. 

Wool  fat,  252,  261. 

Wool,  glass,  590. 

Wool,  mineral,  251. 

Wool,  oil,  308. 

Wool,  steel,  591. 

Woolen  bag  diaphragm,  537. 

Worms,  389. 

Woronin,  12,  131,  424. 

Wussow,  531. 

Xylene,  426,  434. 
Xylenol,  116. 

Yarn-carrying  catalyzer,  56. 

Yocum,  407. 

Yokohama  Fish  Oil  Co.,  589. 

Zeiss  butter  refractometer,  281. 
Zelinski,  257,  424, 


Zeolite,  189,  260. 

Zeolite,  artificial,  256,  261. 

Zeppelin,  440. 

Zerning,  438. 

Zinc,  173,  246,  248,  254,  265,  267,  273r 

422,  437,  519,  522. 
Zinc-aluminum-tin  alloy,  525. 
Zinc  anode,  274. 

Zinc  by-product,  recovery  of,  515. 
Zinc  carbonate,  168,  248. 
Zinc  chloride,  164. 
Zinc  chloride  process,  3. 
Zinc-copper,  208. 
Zinc  dust,  10,  433,  526. 
Zinc  dust  and  calcium  hydrate,  520. 
Zinc  formate,  78,  79,  130,  140. 
Zinc  hydrate,  264. 
Zinc  oxide,  248,  262,  448,  455,  515. 
Zinc  sulphate,  515. 
Zinc-sulphuric  acid  for  making  hydrogen, 

cost  of,  518. 
Zirconia,  427. 
Zirconium,  168,  256,  264. 
Zirconium  nitrate,  456. 
Zirconium  oxide,  119,  251. 
Zirconium  purifier,  600. 
Ziirrer,  2,  608,  612. 
Zvjagin,  170, 


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Bedell,  F.,  and  Pierce,  C.  A.    Direct  and  Alternating  Current  Manual. 

8vo,  2  oo 

Beech,  F.    Dyeing  of  Cotton  Fabrics 8vo,  7  50 

—  Dyeing   of   Woolen   Fabrics. 8vo,  *4  25 

Begtrup,  J.     The  Slide  Valve 8vo,  *2  oo 

Beggs,  G.  E.    Stresses  in  Railway  Girders  and  Bridges (In  Press.) 

Bender,  C.  E.     Continuous  Bridges.     (Science  Series  No.  26.) i6mo,  o  50 

—  Proportions  of  Pins  used  in  Bridges.     (Science  Series  No.  4.) 

i6mo,  o  50 

Bengough,  G.  D.    Brass.     (Metallurgy  Series.) (In  Press.) 

Bennett,  H.  G.  The  Manufacture  of  Leather — 8vo,  *5  oo 

Bernthsen,    A.      A  Text  -  book  of  Organic  Chemistry.      Trans,  by  G. 

M'Gowan    i2mo,  *$  oo 

Bersch,  J.     Manufacture  of  Mineral  and  Lake  Pigments.     Trans,  by  A.  C. 

Wright 8vo, 

Bertin,  L.  E.     Marine  Boilers.     Trans,  by  L.  S.  Robertson 8vo,  5  oo 

Beveridge,  J.     Papermaker's  Pocket  Book i2mo,  *4  oo 

Binnie,  Sir  A.     Rainfall  Reservoirs  and  Water  Supply 8vo,  *3  oo 

Binns,  C.  F.    Manual  of  Practical  Potting 8vo,  *io  oo 

—  The  Potter's  Craft ; i2mo,  *2  oo 

Birchmore,  W.  H.    Interpretation  of  Gas  Analysis I2mo,  *i  25 

Blaine,  R.  G.    The  Calculus  and  Its  Applications 121110,  *i  75 

Blake,  W.  H.    Brewers*  Vade  Mecum 8vo,  *4  oo 

Blanchard,  W.  M.    Laboratory  Exercises  in  General  Chemistry.  .12010,  i  oo 
Blasdale,  W.  C.     Quantitative  Chemical  Analysis.      (Van  Nostrand's 

Textbooks.) i2mo,  *2  50 

Bligh,  W.  G.    The  Practical  Design  of  Irrigation  Works 8vo, 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG         5 

Bloch,  L.     Science  of  Illumination.     Trans,  by  W.  C.  Clinton 8vo,  *2  50 

Blok,  A.     Illumination   and  Artificial   Lighting i2mo,  2  25 

Bliicher,  H.     Modern  Industrial  Chemistry.     Trans,  by  J.  P.  Millington. 

bvo,  *7  50 

Blyth,  A.  W.     Foods :  Their  Composition  and  Analysis 8vo,  7  50 

—  Poisons:    Their   Effects  and  Detection 8vo,  8  50 

Bockmann,    F.      Celluloid i2ino,  *s  oo 

Bodmer,  G.  R.     Hydraulic  Motors  and  Turbines i2mo,  5  oo 

Boileau,  J.  T.     Traverse  Tables 8vo,  5  oo 

Bonney,  G.  E.    The  Electro-platers'  Handbook i2mo,  i  50 

Booth,  N.     Guide  to  the  Ring-spinning  Frame i2mo,  *2  oo 

Booth,  W.  H.     Water  Softening  and  Treatment 8vo,  *2  50 

—  Superheaters  and  Superheating  and  Their  Control 8vo,  *i  50 

Bottcher,  A.     Cranes:   Their  Construction,  Mechanical  Equipment  and 

Working.     Trans,  by  A.  Tolhausen 4to,  *io  oo 

Bottler,  M.     Modern  Bleaching  Agents.     Trans,  by  C.  Salter.  . .  .i2mo,  *3  oo 

Bottone,  S.  R.     Magnetos  for  Automobilists I2mo,  *i  oo 

—  Electro-Motors,  How  Made  and  How  Use i2mo,  i  oo 

Boulton,  S.  B.     Preservation  of  Timber.    (Science  Se'ies  No.  82.) .  i6mo,  050 

Bourcart,  E.     Insecticides,   Fungicides  and   Weedkillers 8vo,  *y  50 

Bourgougnon,  A.    Physical  Problems.    (Science  Series  No.  113.).  i6mo,  050 
Bourry,  E.     Treatise  on  Ceramic  Industries.     Trans,  by  A.  B.  Searle. 

8vo,  *7  25 

Bowie,  A.  J.,  Jr.     A  Practical  Treatise  on  Hydraulic  Mining 8vo,  5  oo 

Bowles,  O.    Tables  of  Common  Rocks.    (Science  Series  No.  I25.).i6mo,  o  50 

Bowser,  E.  A.     Elementary  Treatise  on  Analytic  Geometry i2mo,  i  75 

—  Elementary  Treatise  on  the  Differential  and  Integral  Calculus .  i2mo,  2  25 
Elementary  Treatise  on  Analytic  Mechanics i2mo,  3  oo 

—  Elementary  Treatise  on  Hydro-mechanics i2mo,  2  50 

—  A  Treatise  on  Roofs  and  Bridges i2mo,  *2  25 

Boycott,  G.  W.  M.     Compressed  Air  Work  and  Diving 8vo,  *4  25 

Bradford,  G.,  2nd.    Whys  and  Wherefores  of  Navigation i2mo.  2  oo 

—  Sea  Terms  and  Phrases i2mo,  fabrikoid  (In  Press.} 

Bragg,  E.  M.     Marine  Engine  Design I2mo,  *2  oo 

—  Design  of  Marine  Engines  and  Auxiliaries 8vo,  *$  oo 

Brainard,  F.  R.     The  Sextant.     (Science  Series  No.  101.) i6mo, 

Brassey's    Naval   Annual   for   1915.     War   Edition .  ...8vo,  A  oo 

Briggs,  R.,  and  Wolff,  A.  R.     Steam-Heating      (Science  Series  No. 

68. ) i6mo,  o  50 

Bright,  C.     The  Life  Story  of  Sir  Charles  Tilso.i  Bright 8vo,  *4  50 

—  Telegraphy,  Aeronautics  and  War 8vo,  6  oo 

Brislee,  T.  J.     Introduction  to  the  Study  of  Fuel.     (Outlines  of  Indus- 
trial Chemistry.) 8vo,  *s  oo 

Broadfoot,  S.  K.     Motors:  Secondary  Batteries.     (Installation  Manuals 

Series.) i2mo,  *o  75 

Broughton,  H.  H.     Electric  Cranes  and  Hoists 

Brown,  G.     Healthy  Foundations.     (Science  Series  No.  80  ) i6mo,  o  50 

Brown,  H.     Irrigation 8vo,  *s  oo 

Brown,  H.     Rubber 8vo,  *2  oo 

W.  A.     Portland   Cement  Industry 8vo,  3  oo 

Brown,    Wm.    N.      Dipping,    Burnishing,    Lacquering    and    Bronzing 

Brass  Ware    i2mo,  *a  oo 

Handbook   on    Japanning i2mo,  :|  2  50 


6          D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Brown,  Wm.  N.     The  Art  of  Enamelling  on  Metal i2mo,  *a  25 

—  House  Decorating  and  Painting iamo,  *2  25 

. History  of  Decorative  Art , i2mo,  *i  25 

Workshop   Wrinkles    8vo,  *i  75 

Browne,  C.  L.    Fitting  and  Erecting  of  Engines 8vo,  *i  50 

Browne,  R.  E.     Water  Meters.     (Science  Series  No.  81.) i6mo,  o  50 

Bruce,  E.  M.    Detection  of  Common  Food  Adulterants. i2mo,  i  25 

Brunner,  R.     Manufacture  of  Lubricants,  Shoe  Polishes  and  Leather 

Dressings.     Trans,  by  C.  Salter 8vo,  *4  50 

Buel,  R.  H.     Safety  Valves.     (Science  Series  No.  21.) i6mo,  o  50 

Bunkley,  J.  W.     Military  and  Naval  Recognition  Book i6mo,  i  oc 

Burley,  G.  W.     Lathes,  Their  Construction  and  Operation i2mo,  2  25 

Machine  and  Fitting  Shop  Practice i2mo,  2  50 

—  Testing   of   Machine   Tools i2mo,  2  50 

Burnside,    W.     Bridge    Foundations i2mo,  *i  50 

Burstall,  F.  W.    Energy  Diagram  for  Gas.     With  Text .8vo,  i  50 

Diagram.     Sold  separately *i  oo 

Burt,  W.  A.     Key  to  the  Solar  Compass i6mo,  leather,  2  50 

Buskett,   E.   W.     Fire   Assaying i2mo,  *i  25 

Butler,  H.  J      Motor   Bodies  and   Chassis 8vo,  *s  oo 

Byers,  H.  G.,  and  Knight,  H.  G.     Notes  on  Qualitative  Analysis 8vc,  *i  50 

Cain,  W.    Brief  Course  IP  the  Calculus I2mo,  *i  75 

—  Elastic  Arches.     (Science  Series  No.  48.) i6mo,  o  50 

• Maximum  Stresses.     (Science  Series  No.  38.) .  ..." i6mo,  o  50 

——  Practical  Designing  Retaining  of  Walls.     (Science  Series  No.  3.) 

i6mo,  o  50 
— —  Theory    of    Steel-concrete    Arches   and    of   Vaulted     Structures. 

(Science    Series    No.    42.) i6mo,  o  75 

• Theory  of  Voussoir  Arches.     (Science  Series  No.  12.) i6mo,  o  50 

• Symbolic  Algebra.     (Science  Series  No.  73.) i6mo,  o  50 

Calvert,    G.   T.     The   Manufacture    of    Sulphate    of    Ammonia    and 

Crude  Ammonia i2mo,  4  oo 

Carey,  A.  E.,  and  Oliver,  F.  W.     Tidal  Lands 8vo,  5  oo 

Carpenter,  F.  D.    Geographical  Surveying.    (Science  Series  No.  37.).i6mo, 

Carpenter,  R.  C.,  and  Diederichs,  H.     Internal  Combustion  Engines. .  8vo,  *5  oo 

Carter,  H.  A.    Ramie  (Rhea),  China  Grass i2mo,  *3  oo 

Carter,  H.  R.     Modern  Flax,  Hemp,  and  Jute  Spinning 8vo,  *4  50 

—  Bleaching,  Dyeing  and  Finishing  of  Fabrics .  .8vo,  *i  25 

Cary,  E.  R.     Solutiom  of  Railroad  Problems  with  the  Slide  Rule.  .  i6mo,  *i  oo 

Casler,  M.  D.    Simplified  Reinforced  Concrete  Mathematics i2mo,  *i  oo 

Cathcart,  W.  L.     Machine  Design.     Part  I.  Fastenings 8vo,  *3  oo 

Cathcart,  W.  L.,  and  Chaffee,  J.  I.     Elements  of  Graphic  Statics .  .  .8vo,  *3  oo 

—  —  Short  Course  in  Graphics I2mo,  i  50 

Caven,  R.  M.,  and  Lander,  G.  D.     Systematic  Inorganic  Chemistry. i2mo,  *2  oo 

Chalkley,  A.  P.     Diesel  Engines 8vo,  *4  oo 

Chalmers.  T.  W.     The  Production  and  Treatment  of  Vegetable  Oils, 

4to,  7  50 

Chambers'  Mathematical  Tables 8vo,  i  75 

Chambers,  G.  F.     Astronomy i6mo,  *i  50 

Chappel,  E.    Five  Figure  Mathematical  Tables 8vo,  *2  oo 

Charnock,    Mechanical    Technology 8vo,  *3  oo 

Charpentier,    P.     Timber 8vo,  *7  25 

Chatley,  H.     Principles  and  Designs  of  Aeroplanes.     (Science  Series 

No.  126) i6mo,  o  50 

How  to  Use  Water  Power i2mo,  *i  50 

Gyrostatic  Balancing    8vo,  *i  25 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG         7 

Child,  C.  D.     Electric  Arc 8vo,  *a  oo 

Christian,    M.      Disinfection    and    Disinfectants.      Trans,    by    Chas. 

Salter ismo,      300 

Christie,  W.  W.     Boiler-waters,  Scale,  Corrosion,  Foaming 8vo,  *3  oo 

Chimney  Design  and  Theory 8vo,  *3  oo 

—  Furnace  Draft.     (Science  Series  No.  123.) i6mo,  o  50 

—  Water:  Its  Purification  and  Use  in  the  Industries 8vo,  *2  oo 

Church's  Laboratory  Guide.    Rewritten  by  Edward  Kinch 8vo,  *i  50 

Clapham,  J.  H.     Woolen  and  Worsted  Industries 8vo,  200 

Clapperton,  G.     Practical  Papermaking 8vo,  2  50 

Clark,  A.  G.     Motor  Car  Engineering. 

Vol.    I.     Construction *4  oo 

Vol.  II.     Design 8vo,  *3  oo 

Clark,  C.  H.     Marine  Gas  Engines.     New  Edition 2  oo 

Clark,  J.  M.     New  System  of  Laying  Out  Railway  Turnouts I2mo,  i  oo 

Clarke,  J.  W.,  and  Scott,  W.    Plumbing  Practice. 

Vol.      I.     Lead  Working  and  Plumbers'  Materials 8vo,  *4  oo 

Vol.    II.    Sanitary  Plumbing  and  Fittings (In  Press.} 

Vol.  III.     Practical  Lead  Working  on  Roofs (In  Press.) 

Clarkson,  R.  B.     Elementary  Electrical  Engineering (In  Press.) 

Clausen-Thue,  W.     A  B   C   Universal   Commercial   Telegraphic   Code. 
Sixth  Edition (In  Press.} 

Clerk,  D.,  and  Idell,  F.  E.     Theory  of  the  Gas  Engine.     (Science  Series 

No.  62.) i6mo,  o  50 

Clevenger,  S.  R.     Treatise  on  the  Method  of  Government  Surveying. 

i6mo,   morocco,  2  50 

Clouth,  F.     Rubber,  Gutta-Percha,  and  Balata 8vo,  *6  oo 

Cochran,  J.    Concrete  and  Reinforced  Concrete  Specifications 8vo,  *2  50 

Inspection  of  Concrete  Construction 8vo,  *4  oo 

-  Treatise  on  Cement  Specifications 8vo,  *i  oo 

Cocking,  W.  C.     Calculations  for  Steel-Frame  Structures T2mo,  *s  oo 

Coffin,  J.  H.  C.   Navigation  and  Nautical  Astronomy.  i2mo  (In  Press) 
Colburn,  Z.,  and  Thurston,  R.  H.     Steam  Boiler  Explosions.     (Science 

Series  No.  2.) i6mo,  o  50 

Cole,  R.  S.     Treatise  on  Photographic  Optics i2mo,  i  50 

Coles-Finch,  W.     Water,  Its  Origin  and  Use 8vo,  *$  oo 

Collins,  C.  D.    Drafting  Room  Methods,  Standards  and  Forms 8vo,  2  oo 

Collins,  J.  E.    Useful  Alloys  and  Memoranda  for  Goldsmiths,  Jewelers. 

i6mo,  o  50 

Collis,  A.  G.     High  and  Low  Tension  Switch-Gear  Design 8vo,  *3  50 

Switchgear.      (Installation    Manuals   Series.) i2mo,  *p  50 

Colver,  E.  D.  S      High  Explosives 8vo,  20  oo 

Comstock,  D.  F.,  and  Troland,  L.  T.     The  Nature  of  Electricity  and 

Matter  8vo,  *2  oo 

Coombs,  H.  A.     Gear  Teeth.     (Science  Series  No.  120.) i6mo,  o  50 

Cooper,  W.  R.    Primary  Batteries 8vo,  *6  oo 

Copperthwaite,  W.  C.     Tunnel  Shields 4to,  *p  oo 

Corfield,  W.  H.     Dwelling  Houses.     (Science  Series  No.  50.) . . .  .i6mo,  o  50 

— -  Water  and  Water-Supply.     (Science  Series  No.  17.) i6mo,  o  50 

Cornwall,  H.  B.     Manual  of  Blow-pipe  Analysis 8vo,  *2  50 

Cowee,  G.  A.    Practical  Safety  Methods  and  Devices 8ve,  *3  oo 


8          D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Cowell,  W.  B.     Pure  Air,  Ozone,  and  Water i?.mo,  *3  oo- 

Craig,  J.  W.,  and  Woodward,  W.  P.     Questions  and  Answers  About 

Electrical  Apparatus i2mo,  leather,  i  50 

Craig,  T.     Motion  of  a  Solid  in  a  Fuel.     (Science  Series  No.  49.) .  i6mo,  o  50 

Wave  and  Vortex  Motion.     (Science  Series  No.  43.) i6mo,  o  50 

Cramp,  W.     Continuous  Current  Machine  Design 8vo,  *2  50 

Crehore,  A.  C.     Mystery  of  Matter  and  Energy 8vo,  i  oo 

Creedy,  F.     Single  Phase  Commutator  Motors ; 8vo,  *2  oo 

Crocker,  F.  B.    Electric  Lighting.    Two  Volumes.    8vo. 

Vol.   I.    The  Generating  Plant 3  o> 

Vol.  II.    Distributing  Systems  and  Lamps 

Crocker,  F.  B.,  and  Arendt,  M.    Electric  Motors 8vo,  *2  50 

Crocker,  F.  B.,  and  Wheeler,  S.  S.    The  Management  of  Electrical  Ma- 
chinery  i2me,  *i  oo 

Crosby,  E.  U.,  Fiske,  H.  A.,  and  Forster,  H.  W.     Handbook  of  Fire 

Protection i2mo,  400 

Cross,  C.  F.,  Bevan,  E.  J.,  and  Sindall,  R.  W.    Wood  Pulp  and  Its  Applica- 
tions.    (Westminster  Series.) 8vo,  *2  oo> 

Crosskey,  L.  R.     Elementary  Perspective 8vo,  i  25 

Crosskey,  L.  R.,  and  Thaw,  J.    Advanced  Perspective 8vo,  i  50 

Culley,  J.  L.     Theory  of  Arches.     (Science  Series  No.  87.) i6mo,  o  50 

Cushing,  H.  C.,  Jr*.,  and  Harrison,  N.    Central  Station  Management.  ..  *2  oo 

Dadourian,  H.  M.    Analytical  Mechanics i2mo,  *3  oa 

Dana,  R.  T.    Handbook  of  Construction  plant i2mo,  leather,  *s  oo 

Danby,  A.     Natural  Rock  Asphalts  and  Bitumens 8vo,  *2  50 

Davenport,  C.     The  Book.     (Westminster  Series.) 8vo,  *2  oo 

Davey,  N.    The  Gas  Turbine 8vo,  *4  oo 

Davjes,  F.  H.     Electric  Power  and  Traction 8vo,  *2  oo 

—  Foundations  and  Machinery  Fixing.     (Installation  Manual  Series.) 

i6mo,  *i  oo 

Deerr,   N.     Sugar   Cane 8vo,  9  oo 

Deite,  C.     Manual  of  Soapmaking.     Trans,  by  S.  T.  King 410, 

De  la  Coux,  H.  The  Industrial  Uses  of  Water.  Trans,  by  A.  Morris. Svo,  *6  oo 

Del  Mar,  W.  A.    Electric  Power  Conductors Svo,  *2  oo 

Denny,  G.  A.    Deep-level  Mines  of  the  Rand 410,  *io  oo 

Diamond  Drilling  for  Gold *5  oo 

De  Roos,  J.  D.  C.     Linkages.     (Science  Series  No.  47.) i6mo,  o  50 

Derr,  W.  L.     Block  Signal  Operation ., . . .  Oblong  i2mo,  *i  50 

Maintenance-of-Way  Engineering (In  Preparation.) 

Desaint,  A.     Three  Hundred  Shades  and  How  to  Mix  Them Svo,  *io  oo 

De  Varona,  A.     Sewer  Gases.     (Science  Series  No.  55.) i6mo,  o  50 

Devey,  R.  G.     Mill  and  Factory  Wiring.     (Installation  Manuals  Series.) 

izmo,  *i  oo 

Dibdin,  W.  J.     Purification  of  Sewage  and  Water ? . Svo,  6  50 

Dichmann,  Carl.     Basic  Open-Hearth  Steel  Process i2mo,  *3  50 

Dieterich,  K.     Analysis  of  Resins,  Balsams,  and  Gum  Resins. ..  .8vo,  *3  75 

Dilworth,  E.  C.     Steel  Railway  Bridges 4to.  *4  oo 

Dinger,  Lieut.  H.  C.    Care  and  Operation  of  Naval  Machinery. .  .i2mo,  *s  oo 
Dixon,  D.  B.     Machinist's  and  Steam  Engineer's  Practical  Calculator. 

i6mo,  morocco,  i  25 
Dodge,  G.  F.    Diagrams  for  Designing  Reinforced  Concrete  Structures, 

folio,  *4  oo 

Dommett,  W.  E.    Motor  Car  Mechanism i2mo,    *2  25 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG          9 

Dorr,  B.  F.     The  Surveyor's  Guide  and  Pocket  Table-book. 

i6mo,  morocco,  2  oo 

Draper,  C.  H.     Elementary  Text-book  of  Light,  Heat  and  Sound  .  .  i2mo,  i  oo 

—  Heat  and   the   Principles   of   Thermo-dynamics izmo,  *2  oo 

Draper,    E.   G.     Navigating   the   Ship i2mo,  i  50 

Dron,  R.  W.     Mining  Formulas 12010,  i  oo 

Dubbel,  H.     High  Power  Gas  Engines 8vo,  *s  oo 

Dumesny,  P.,  and  Noyer,  J.     Wood  Products,  Distillates,  and  Extracts. 

8vo,  *6  25 
Duncan,  W.  G.,  and  Penman,  D.  The  Electrical  Equipment  of  Collieries. 

8vo,  *6  75 

Dunkley,  W.  G.  Design  of  Machine  Elements.  Two  Volumes. 8vo,  each,  2  50 
Dunstan,  A.  E.,  and  Thole,  F.  B.  T.  Textbook  of  Practical  Chemistry. 

izmo,  *i  40 

Durham,  H.  W.     Saws 8vo,  2  50 

Duthie,  A.  L.     Decorative  Glass  Processes.     (Westminster  Series.)  .8vo,  *2  oo 

Dwight,  H.  B.     Transmission  Line  Formulas 8vo,  *2  oo 

Dyson,  S.  S.     Practical  Testing  of  Raw  Materials 8vo,  *5  oo 

Dyson,  S.  S.,  and  Clarkson,  S.  S.     Chemical  Works 8vo,  *n  50 

Eccles,  W.  H.     Wireless  Telegraphy  and  Telephony i2mo,  *8  80 

Eck,  J.     Light,  Radiation  and  Illumination.     Trans,  by  Paul  Hogner, 

8vo,  *2  50 

Eddy,  H.  T.    Maximum  Stresses  under  Concentrated  Loads 8vo,  i  50 

Eddy,  L.  C.     Laboratory  Manual  of  Alternating  Currents i2mo,  o  50 

Edelman,  P.  Inventions  and  Patents i2mo,  *i  50 

Edgcumbe,  K.     Industrial  Electrical  Measuring  Instruments 8vo, 

(In  Press.) 

Edler,  R.     Switches  and  Switchgear.     Trans,  by  Ph.  Laubach.  .  ,8vo,  *4  oo 

Eissler,  M.     The  Metallurgy  of  Gold 8vo,  g  oo 

The  Metallurgy  of  Silver 8vo,  4  oo 

—  The   Metallurgy   of   Argentiferous   Lead 8vo,  6  25 

A  Handbook  on  Modern  Explosives 8vo,  5  oo 

Ekin,  T.  C.     Water  Pipe  and  Sewage  Discharge  Diagrams folio,  *3  oo 

Electric  Light  Carbons,  Manufacture  of 8vo,  i  oo 

Eliot,  C.  W.,  and  Storer,  F.  H.     Compendious  Manual  of  Qualitative 

Chemical  Analysis i2mo,  *i  25 

Ellis,  C.     Hydrogenation  of  Oils 8vo,  7  50 

—  Ultraviolet   Light,   Its   Applications   in   Chemical   Arts izmo, 

(In  Prrsrt 

Ellis,  G.     Modern  Technical  Drawing 8vo,  *2  oo 

Ennis,  Wm.  D.     Linseed  Oil  and  Other  Seed  Oils 8vo,  *4  oo 

Applied  Thermodynamics 8vo,  *4  50 

Flying  Machines  To-day 12010,  *i  50 

Vapors  for  Heat  Engines i2mo,  *i  oo 

Ermen,  W.  F.  A.     Materials  Used  in  Sizing 8vo,  *2  oo 

Erwin,  M.     The  Universe  and  the  Atom i2mo,  *2  oo 

Evans,  C.  A.     Macadamized  Roads (In  Press.) 

Ewing,  A,  J,    Magnetic  Induction  in  Iron 8vo,  *4  oo 

Fairchild,  J.  F.     Graphical  Compass  Conversion  Chart  and  Tables...  o  50 

Fame,  J.     Notes  on  Lead  Ores i2mo,  *o  50 

Notes  on   Pottery  Clays i2mo,  *2  25 


10       D.  V.  N  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Fairley,  W.,  and  Andre,  Geo.  J.    Ventilation  of  Coal  Mines.     (Science 

Series  No.  58.) i6mo,  o  50 

Fairweather,  W.  C.    Foreign  and  Colonial  Patent  Laws 8vo,  *3  oo 

Falk,  M.  S.     Cement  Mortars  and  Concretes 8vo,  *2  50 

Fanning,  J.  T.     Hydraulic  and  Water-supply  Engineering 8vo,  *5  oo 

Fay,  I.  W.     The  Coal-tar  Colors 8vo,  *4  oo 

Fernbach,  R.  L.     Glue  and  Gelatine 8vo,  *3  oo 

Findlay,  A.    The  Treasures  of  Coal  Tar lamo,  2  oo 

Firth,  J.  B.    Practical  Physical  Chemistry i2mo,  i  25 

Fischer,  E.    The  Preparation  of  Organic  Compounds.    Trans,  by  R.  V. 

Stanford i2mo,  *i  25 

Fish,  J.  C.  L.    Lettering  of  Working  Drawings Oblong  8vo,  i  oo 

Mathematics  of  the  Paper  Location  of  a  Railroad,  .paper,  i2mo,  *o  25 

Fisher,  H.  K.  C.,  and  Darby,  W.  C.    Submarine  Cable  Testing  .  . .  .8vo,  *3  50 
Fleischmann,  W.    The  Book  of  the  Dairy.     Trans,  by  C.  M.  Aikman. 

8vo,  4  50 
Fleming,  J.  A.     The  Alternate-current  Transformer.     Two  Volumes.  8vo. 

Vol.    I.     The  Induction  of  Electric  Currents *5  50 

Vol.  II.    The  Utilization  of  Induced  Currents 5  50 

Propagation  of  Electric  Currents 8vo,  *s  oo 

A  Handbook  for  the  Electrical  Laboratory  and  Testing  Room.    Two 

Volumes 8vo,  each,  *6  50 

Fleury,  P.     Preparation  and  Uses  of  White  Zinc   Paints 8vo,  *s  50 

Flynn,  P.  J.    Flow  of  Water.     (Science  Series  No.  84.) i2mo,  o  50 

—  Hydraulic  Tables.     (Science  Series  No.  66.) i6mo,  o  50 

Forgie,  J.     Shield  Tunneling 8vo.    (In   Press.} 

Foster,  H.  A.    Electrical  Engineers'  Pocket-book.     (Seventh  Edition.) 

i2mo,  leather,  5  oo 

Engineering  Valuation  of  Public  Utilities  and  Factories 8vo,  *3  oo 

Handbook  of  Electrical  Cost  Data 8vo  (In  Press.) 

Fowle,  F.  F.     Overhead  Transmission  Line  Crossings i2mo,  *i  50 

The  Solution  of  Alternating  Current  Problems 8vo  (In  Press.) 

Fox,  W.  G.     Transition  Curves.     (Science  Series  No.  no.) i6mo,  o  50 

Fox,  W.,  and  Thomas,  C.  W.    Practical  Course  in  Mechanical  Draw- 
ing   i2mo,  i  25 

Foye,  J.  C.     Chemical  Problems.     (Science  Series  No.  69.) i6mo,  o  50 

Handbook  of  Mineralogy.     (Science  Series  No.  86.) i6mo,  o  50 

Francis,  J.  B.    Lowell  Hydraulic  Experiments 4to,  15  oo 

Franzen,  H.     Exercises  in  Gas  Analysis i2mo,  *i  oo 

Freudemacher,   P.   W.    Electrical   Mining  Installations.     (Installation 

Manuals  Series.) i2mo,  *i  oo 

Friend,  J.  N.     The  Chemistry  of  Linseed  Oil i2mo,  i  oo 

Frith,  J.     Alternating  Current  Design 8vo,  *2  50 

Fritsch,  J.     Manufacture  of  Chemical  Manures.    Trans,  by  D.  Grant. 

8vo,  *6  50 

Frye,  A.  I.     Civil  Engineers'  Pocket-book i2mo,  leather,  *5  oo 

Fuller,  G.  W.    Investigations  into  the  Purification  of  the  Ohio  River. 

4to,  *io  oo 
Furnell,  J.    Paints,  Colors,  Oils,  and  Varnishes 8vo. 

Gairdner,  J.  W.  I.     Earthwork 8vo  \In  Press.) 

Gant,  L.  W.     Elements  of  Electric  Traction 8vo,  *2  50- 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  1.1 

Garcia,  A.  J.  R.  V.     Spanish-English  Railway  Terms 8vo,  *4  50 

Gardner,  H.   A.     Paint   Researches,   and  Their  Practical   Applications, 

8vo,  *s  oo 
Garforth,  W.  E.     Rules  for  Recovering  Coal  Mines  after  Explosions  and 

Fires izmo,  leather,  i  50 

Garrard,  C.  C.    Electric  Switch  and  Controlling  Gear 8vo,  *6  oo 

Gaudard,  J.  Foundations.  (Science  Series  No.  34.) i6mo,  050 

Gear,  H.  B.,  and  Williams,  P.  F.  Electric  Central  Station  Distribution 

Systems  8vo,  *3  50 

Geerligs,  H.  Cj  P.  Cane  Sugar  and  Its  Manufacture 8vo,  *6  oo 

— —  Chemical  Control  in  Cane  Sugar  Factories 4to,  5  oo 

Geikie,  J.  Structural  and  Field  Geology 8vo,  *4  oo 

Mountains.  Their  Growth,  Origin  and  Decay 8vo,  *4  oo 

—  The  Antiquity  of  Man  in  Europe 8vo,  *3  oo 

Georgi,  F.,  and  Schubert,  A.  Sheet  Metal  Working.  Trans,  by  C. 

Salter 8vo,  4  25 

Gerhard,  W.  P.  Sanitation,  Watersupply  and  Sewage  Disposal  of  Country 

Houses i2mo,  *2  oo 

Gas  Lighting  (Science  Series  No.  in.) i6mo,  o  50 

Household  Wastes.  (Science  Series  No.  97.) i6mo,  o  50 

House  Drainage.  (Science  Series  No.  63.) i6mo,  o  50 

~— -  Sanitary  Drainage  of  Buildings.  (Science  Series  No.  93.)  i6mo,  o  50 

Gerhardi,  C.  W.  H.  Electricity  Meters 8vo,  *6  oo 

Geschwind,  L.  Manufacture  of  Alum  and  Sulphates.  Trans,  by  C. 

Salter 8vo,  *5  oo 

Gibbings,  A.  H.  Oil  Fuel  Equipment  for  Locomotives 8vo,  *2  50 

Gibbs,  W.  E.  Lighting  by  Acetylene i2mo,  *i  50 

Gibson,  A.  H.  Hydraulics  and  Its  Application 8vo,  *5  oo 

Water  Hammer  in  Hydraulic  Pipe  Lines 12 mo,  *2  oo 

Gibson,  A.  H.,  and  Ritchie,  E.  G.  Circular  Arc  Bow  Girder 4to,  *3  50 

Gilbreth,  F.  B.  Motion  Study I2mo,  *2  oo 

Bricklaying  System  8vo,  *3  oo 

Field  System  12010,  leather,  *3  oo 

Primer  of  Scientific  Management. i2mo,  *i  oo 

Gillette,  H.  P.  Handbook  of  Cost  Data i2mo,  leather,  *s  oo 

Reck  Excavation  Methods  and  Cost i2mo,  *5  oo 

and  Dana,  R.  T.  Cost  Keeping  and  Management  Engineering .  8vo,  *3  50 

and  Hill,  C.  S.  Concrete  Construction,  Methods  and  Cost.  ..  .8vo,  *5  oo 

Gillmore,  Gen.  Q.  A.  Roads,  Streets,  and  Pavements i2mo,  i  25 

Godfrey,  E.  Tables  for  Structural  Engineers i6mo,  leather,  *2  50 

Golding,  H.  A.  The  Theta-Phi  Diagram i2mo,  *2  oo 

Goldschmidt,  R.  Alternating  Current  Commutator  Motor 8vo,  *3  oo 

Goodchild,  W.  Precious  Stones.  (Westminster  Series.) 8vo,  *2  oo 

Goodell,  J.  M.  The  Location,  Construction  and  Maintenance  of 

Roads 8vo,  i  50 

Goodeve,  T.  M.  Textbook  on  the  Steam-engine i2mo,  2  oo 

Gore.  G.  Electrolytic  Separation  of  Metals 8vo,  *3  50 

Gould,  E.  S.  Arithmetic  of  the  Steam-engine i2tno,  i  oo 

Calculus.  (Science  Series  No.  112.) i6mo,  o  50 

High  Masonry  Dams.  (Science  Series  No.  22.) i6mo,  o  50 

Gould,  E'  S.  Practical  Hydrostatics  and  Hydrostatic  Formulas.  (Science 

Series  No,  117.) i6mo,  o  50 


12        D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Gratacap,  L.  P.    A  Popular  Guide  to  Minerals 8vo,  *2  oo 

Gray,  J.     Electrical  Influence  Machines i2mo,  2  oo 

—  Marine  Boiler  Design i2mo,  *i  25 

Greenhill,  G.     Dynamics  of  Mechanical  Flight 8vo,  *2  50 

Gregorius,  R.     Mineral  Waxes.     Trans,  by  C.  Salter i2mo,  *3  50 

Grierson,  R.     Some  Modern  Methods  of  Ventilation 8vo,  *3  oo 

Griffiths,  A.  B.     A  Treatise  on  Manures i2mo,  3  oo 

Dental   Metallurgy    8vo,  *4  25 

Gross,  E.     Hops 8v«,  *6  25 

Grossman,  J.     Ammonia  and  Its  Compounds i2mo,  *i  25 

Groth,   L.  A.     Welding  and  Cutting  Metals  by   Gases  or  Electricity. 

(Westminster  Series) 8vo,  *2  oo 

Grover,  F.     Modern  Gas  and  Oil   Engines 8w,  *3  oo 

Gruner,  A.     Power-loom  Weaving 8vo,  *3  oo 

Gnmsky,  C.  E.     Topographic  Stadia  Surveying i6mo,  2  oo 

Giildner,  Hugo.     Internal  Combustion  Engines.     Trans,  by  H.  Diederichs. 

4to,  *i5  oo 

Anther,  C.  0.     Integration 8vo,  *i  25 

Guraen,  !3.  L.     Traverse  Tables folio,  half  morocco,  *7  50 

Guy,  A.  E.     Experiments  on  the  Flexure  of  Beams 8vo,  *i  25 

Haenig,   A.     Emery   and    Emery   Industry 8vo,  *3  oo 

Hainbach,  R.     Pottery  Decoration.    Trans.,  by  C.  Salter i2mo,  *4  25 

Hale,  W.  J.    Calculations  of  General  Chemistry i2mo,  *i  25 

Hall,  C.  H.     Chemistry  of  Paints  and  Paint  Vehicles i2mo,  *2  oo 

Hall,  G.  L.    Elementary  Theory  of  Alternate  Current  Working ....  8vo, 

Hall,  R.  H.     Governors  and  Governing  Mechanism i2mo,  *2  50 

Hall,  W.  S.     Elements  of  the  Differential  and  Integral  Calculus 8vo,  *2  25 

Descriptive  Geometry .  .8vo  volume  and  a  4to  atlas,  *3  50 

Haller,  G.  F.,  and  Cunningham,  E.  T.     The  Tesla  Coil i2mo,  *i  25 

Halsey,  F.  A.     Slide  Valve  Gears i2mo,  i  50 

•  The  Use  of  the  Slide  Rule.     (Science  Series  No.  114.) i6mo,  o  50 

Worm  and  Spiral  Gearing.     (Science  Series  No.  116.) i6mo,  o  50 

Hancock,  H.     Textbook  of  Mechanics  and  Hydrostatics 8vo,  i  50 

Hancock,  W.  C.  Refractory  Materials.  (Metallurgy  Series.)    (In  Press.} 

Hardy,  E.     Elementary  Principles  of  Graphic  Statics i2mo,  *i  50 

Haring,  H.     Engineering  Law. 

Vol.  I.     Law  of  Contract 8vo,  *4  oo 

Harper,  J.  H.     Hydraulic  Tables  on  the  Flow  of  Water i6mo,  *2  oo 

Harris,  S.  M.    Practical  Topographical  Surveying (In  Press.} 

Harrison,  W.  B.     The  Mechanics'  Tool-book i2mo,  i  50 

Hart,  J.  W.    External  Plumbing  Work 8vo,  *3  25 

Hints   to    Plumbers   on   Joint   Wiping 8vo,  *4  25 

Principles   of   Hot   Water  Supply 8vo,  *4  25 

—  Sanitary    Plumbing   and    Drainage 8vo,  *4  25 

Haskins,  C.  H.     The  Galvanometer  and  Its  Uses i6mo,  i  50 

Hatt,  J.  A.  H.     The  Colorist square  i2mo,  *i  50 

Hausbrand,  E.     Drying  by  Means  of  Air  and  Steam.     Trans,  by  A.  C. 

Wright i2mo,  *3  oo 

Evaporating,  Condensing  and  Cooling  Apparatus.     Trans,  by  A.  C. 

Wright.... 8vo,  *7  25 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  13 

Hausmann,   E.     Telegraph   Engineering 8vo,  *s  oo 

Hausner,  A.     Manufacture  of  Preserved  Foods  and  Sweetmeats.     Trans. 

by  A.  Morris  and  H.  Robson 8vo,  *4  «£ 

Hawkesworth,  J.     Graphical  Handbook  for  Reinforced  Concrete  Design. 

4to,  *2  50 

Hay,  A.     Continuous  Current  Engineering 8vo,  *2  50 

Hayes,  H.  V.    Public  Utilities,  Their  Cost  New  and  Depreciation. .  .8vo,  *2  oo 

—  Public  Utilities,  Their  Fair  Present  Value  and  Return 8vo,  *2  oo 

Heath,  F.  H.    Chemistry  of  Photography 8vo.  (In  Press.) 

Heather,  H.  J.  S.     Electrical  Engineering 8vo,  *3  50 

Heaviside,  O.     Electromagnetic  Theory.      Vols.  I  and  II.  ..  .8vo,  each,  *6  oo 


Vol.  Ill 8vo, 


IO    OO 

Heck,  R.  C.  H.     The  Steam  Engine  and  Turbine 8vo,  *s  50 

Steam-Engine  and  Other  Steam  Motors.    Two  Volumes. 

Vol.    I.     Thermodynamics  and  the  Mechanics 8vo,  *3  50 

Vol.  II.     Form,  Construction,  and  Working 8vo,  *5  oo 

Notes  on  Elementary  Kinematics 8vo,  boards,  *i  oo 

—  Graphics  of  Machine  Forces 8vo,  boards,  *i  oo 

Heermann,  P.    Dyers'  Materials.    Trans,  by  A.  C.  Wright i2mo,  *s  oo 

Heidenreich,    E.    L.      Engineers'    Pocketbook    of    Reinforced    Concrete, 

i6mo,  leather,  *3  oo 

Hellot,  Macquer  and  D'Apligny.   Art  of  Dyeing  Wool,  Silk  and  Cotton.   8vo,  *2  oo 

Henrici,  0.     Skeleton  Structures 8vo,  i  50 

Bering,  C.,  and  Getman,  F.  H.     Standard  Tables  of  Electro-Chemical 

Equivalents    i2mo,  *2  oo 

Bering,  D.  "W.     Essentials  of  Physics  for  College  Students 8vo,  *i  75 

Hering-Shaw,  A.     Domestic  Sanitation  and  Plumbing.     Two  Vols. .  .  8vo,  *s  oo 

Hering-Shaw,  A.     Elementary  Science 8vo,  *2  oo 

Herington,  C.  F.     Powdered  Coal  as  Fuel 8vo,  300 

Herrmann,  G.     The  Graphical  Statics  of  Mechanism.     Trans,  by  A.  P. 

Smith i2mo,  2  oc 

Herzfeld,  J.     Testing  of  Yarns  and  Textile  Fabrics 8vo,  *6  25 

Hildebrandt,  A.     Airships,  Past  and  Present 8vo, 

Hildenbrand,  B.  W.    Cable-Making.     (Science  Series  No.  32.)  .  . .  .i6mo,  o  50 

Hilditch,  T.  P.     A  Concise  History  of  Chemistry i2mo,  *i  50 

Hill,  C.  S.     Concrete   Inspection i6mo,  *i  oo 

Hill,  J.  W.    The  Purification  of  Public  Water  Supplies.    New  Edition. 

(In   Press.) 

—  Interpretation  of  Water  Analysis (In  Press.) 

Hill,  M.  J.  M.     The  Theory  of  Proportion 8vo,  *2  50 

Hillhouse,  P.  A.     Ship  Stability  and,  Trim 8vo,  4  50 

Hiroi.  I.    Plate  Girder  Construction.     (Science  Series  No.  95.).  . .  i6mo,  o  50 

Statically-Indeterminate  Stresses i2mo,  *2  oo 

Hirshfeld,  C.  F.    Engineering  Thermodynamics.  (Science  Series  No.  45.) 

i6mo,  o  50 

Hoar,  A.     The  Submarine  Torpedo  Boat i2mo,  *2  oo 

Hobart,  H.  M.     Heavy  Electrical  Engineering 8vo,  *4  50 

Design  of  Static  Transformers i2mo,  *2  oo 

Electricity 8vo,  *2  oo 

Electric  Trains 8vo,  *2  50 

Electric  Propulsion  of  Ships 8vo,  *2  50 


14       E>.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Hobart,  J.  F.    Hard  Soldering,  Soft  Soldering  and  Brazing i2mo,  *i  oo 

Hobbs,  W.  R.  P.    The  Arithmetic  of  Electrical  Measurements lamo,  o  75 

Hoff,  J.  N.    Paint  and  Varnish  Facts  and  Formulas zamo,  *i  50 

Hole,  W.     The  Distribution  of  Gas 8vo,  *8  50 

Holley,  A.  L.     Railway  Practice folio,  6  oo 

Hopkins,  N.  M.     Model  Engines  and  Small  Boats lamo,  i  25 

Hopkinson,  J.,  Shoolbred,  J.  N.,  and  Day,  R.  E.    Dynamic  Electricity. 

(Science  Series  No.  71.) i6mo,  o  50 

iHorner,  J.     Practical  Ironfounding 8vo,  *2  oo 

Gear  Cutting,  in  Theory  and  Practice 8vo,  *3  oo 

Horniman,  Roy.    How  to  Make  the  Railways  Pay  For  the  War 8vo,  3  oo 

Houghton,  C.  E.    The  Elements  of  Mechanics  of  Materials i2mo,  *2  oo 

Houstoun,  R.  A.    Studies  in  Light  Production i2mo,  2  oo 

Hovenden,  F.     Practical  Mathematics  for  Young  Engineers. ,,..  ,i2mo,  *i  50 

Howe,  G.     Mathematics  for  the  Practical  Man.    i2mo,  *i  25 

Howorth,  J.     Repairing  and  Riveting  Glass,  China  and  Earthenware. 

8vo,  paper,  *i  oo 

Hoyt,  W.  E.     Chemistry  by  Experimentation 8vo,  *o  70 

Hubbard,   E.     The  Utilization  of  Wood-waste 8vo,  *3  oo 

Hiibner,  J.   Bleaching  and  Dyeing  of  Vegetable  and  Fibrous  Materials. 

(Outlines  of  Industrial  Chemistry.) 8vo,  *5  oo 

Hudson,  0.  F.    Iron  and  Steel.    (Outlines  of  Industrial  Chemistry.  ).8vo,  *2  oo 
Humphrey,  J.  C.  W.     Metallography  of  Strain.     (Metallurgy  Series.) 

(In  Press.) 

Humphreys,  A.  C.     The  Business  Features  of  Engineering  Practice.. 8vo.  *i  25 

Hunter,  A.    Bridge  Work 8vo.  (In  Press.) 

Hurst,  G.  H.     Handbook  of  the  Theory  of  Color. 8vo,  *4  25 

—  Dictionary  of  Chemicals  and  Raw  Products 8vo,  *6  25 

— —  Lubricating  Oils,  Fats  and  Greases 8vo,  *7  25 

—  Soaps 8vo,  *7  25 

Hurst,  G.  H.,  and  Simmons,  W.  H.     Textile  Soaps  and  Oils 8vo,  4  25 

Hurst,  H.  E.,  and  Lattey,  R.  T.    Text-book  of  Physics 8vo,  *3  oo 

—  Also   published  in  three  parts. 

Part      I.    Dynamics  and  Heat *i  25 

Part    II.    Sound  and  Light *i  25 

Part  III.    Magnetism  and  Electricity *i  50 

Hutchinson,  R.  W.,  Jr.    Long  Distance  Electric  Power  Transmission. 

i2mo,  *3  oo 

Hutchinson,  R.  W.,  Jr.,  and  Thomas,  W.  A.    Electricity  in  Mining.  i2mo, 

(In  Press.) 
Hutchinson,  W.  B.     Patents  and  How  to  Make  Money  Out  of  Them. 

I2TT10,  I    00 

Hutton,  W.  S.    The  Works'  Manager's  Handbook 8vo,  6  oo 

Hyde,  E.  W.     Skew  Arches.     (Science  Series  No.  15.) i6mo,  o  50 

Hyde,  F.  S.     Solvents,  Oils,  Gums,  Waxes 8vo,  *2  oo 

Induction  Coils.     (Science  Series  No.  53.) i6mo,  o  50 

Ingham,  A.  E.    Gearing.    A  practical  treatise 8vo,  *2  50 

Ingle,  H.     Manual  of  Agricultural  Chemistry 8vo,  *4  25 


D    VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  15 

Inness,  C.  H.    Problems  in  Machine  Design i2mo,  *3  oo 

—  Air  Compressors  and  Blowing  Engines i2mo, 

Centrifugal  Pumps  i2mo,  *3  oo 

The  Fan i2mo,  *4  oo 

Jacob,  A.,  and  Gould,  E.  S.  On  the  Designing  and  Construction  of 

Storage  Reservoirs.  (Science  Series  No.  6) i6mo,  o  50 

Jannettaz,  E.  Guide  to  the  Determination  of  Rocks.  Trans,  by  G.  W. 

Plympton * i2mo,  i  50 

Jehl,  F.     Manufacture  of  Carbons 8vo,  *4  oo 

Jennings,  A.  S.  Commercial  Paints  and  Painting.  (Westminster  Series.) 

8vo,  *4  oo 

Jennison,  F.  H.     The  Manufacture  of  Lake  Pigments 8vo,  *3  oo 

Jepson,  G.     Cams  and  the  Principles  of  their  Construction 8vo,  *i  50 

—  Mechanical  Drawing 8^>  (In  Preparation.) 

Jervis-Smith,   F.   J.     Dynamometers 8vo,  *3  50 

Jockin,  W.     Arithmetic  of  the  Gold  and  Silversmith i2mo,  *i  oo 

Johnson,  J.  H.     Arc  Lamps  and  Accessory  Apparatus.     (Installation 

Manuals  Series.) I2mo,  *o  75 

Johnson,  T.  M.     Ship  Wiring  and  Fitting.     (Installation  Manuals  Series.) 

i2mo,  *o  75 

Johnson,  W.  McA.     The  Metallurgy  of  Nickel (In  Preparation.) 

Johnston,  J.  F.  W.,  and  Cameron,  C.     Elements  of  Agricultural  Chemistry 

and  Geology i2mo,  2  60 

Joly,  J.     Radioactivity  and  Geology i2mo,  -3  oo 

Jones,  H.  C.     Electrical  Nature  of  Matter  and  Radioactivity i2mo,  *2  oo 

Nature   of  Solution 8vo,  *3  50 

—  New  Era  in  Chemistry i2mo,  *2  oo 

Jones,  J.  H.     Tinplate  Industry 8vo,  *3  oo 

Jones,  M.  W.     Testing  Raw  Materials  Used  in  Paint X2mo,  *3  oo 

Jordan,  L.  C.     Practical  Railway  Spiral i2mo,  leather,  *i  50 

Joynson,  F.  H.     Designing  and  Construction  of  Machine  Gearing  .  .8vo,  2  oo 

Jiiptner,  H.  F.  V.    Siderology:  The  Science  of  Iron 8vo,  *6  25 

Kapp,  G.    Alternate  Current  Machinery.     (Science  Series  No.  96.). i6mo,  o  50 

Kapper,  F.     Overhead  Transmission  Lines 4to,  *4  oo 

Keim,  A.  W.    Prevention  of  Dampness  in  Buildings 8vo,  *3  oo 

Keller,  S.  S.     Mathematics  for  Engineering  Students.     1 2mo,  half  leather. 

—  and  Knox,  W.  E.    Analytical  Geometry  and  Calculus *2  oo 

Kelsey,  W.  R.     Continuous-current  Dynamos  and  Motors 8vo,  *2  50 

Kemble,  W.  T.,  and  Underbill,  C.  R.     The  Periodic  Law  and  the  Hydrogen 

Spectrum 8vo,  paper,  *o  50 

Kemp,  J.  F.     Handbook  of  Rocks 8vo,  *i  50 

Kennedy,  A.  B.  W.,  and  Thurston,  R.  H.    Kinematics  of  Machinery. 

(Science  Series  No.  54.) i6mo,  o  50 

Kennedy,  A.  B.  W.,  Unwin,  W.  C.,  and  Idell,  F.  E.     Compressed   Air. 

(Science  Series  No.  106.) l6mo>  o  go 


l£       O.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Kennedy,  R.     Electrical  Installations.    Five  Volumes 4to,  15  oo 

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Principles  of  Aeroplane  Construction 8vo,  *2  oo 

Kennelly,  A.  E.     Electro-dynamic  Machinery 8vo,  i  50 

Kent,  W.     Strength  of  Materials.     (Science  Series  No.  41.) i6mo,  o  50 

Kershaw,  J.  B.  C.     Fuel,  Water  and  Gas  Analysis  .f 8vo,  *2  50 

—  Electrometallurgy.     (Westminster  Series.) 8vo,  *2  oo 

—  The  Electric  Furnace  in  Iron  and  Steel  Production i2mo, 

Electro-Thermal   Methods   of  Iron   and   Steel   Production.  ..  .8vo,  *3  oo 

Kindelan,  J.     Trackman's  Helper 12010,  2  oo 

Kinzbrunner,  C.     Alternate  Current  Windings 8vo,  *i  50 

Continuous  Current  Armatures 8vo,  *i  50 

Testing  of  Alternatin^Current  Machines 8vo,  *2  oo 

Kirkaldy,    A..    W.,    and    Evans,    A.    D.      History    and    Economics    of 

Transport 8vo,  *s  oo 

Kirkaldy,  W.  G.    David  Kirkaldy's  System  of  Mechanical  Testing ..  4to,  10  oo 

Kirkhride,  J.     Engraving  for  Illustration 8vo,  *i  75 

Kirkham,  J.  E.     Structural  Engineering 8vo,  *$  oo 

Kirkwood,  J.  P.     Filtration  of  River  Waters 4to,  7  50 

Kirschke,  A.     Gas  and  Oil  Engines i2mo,  *i  50 

Klein,  J.  F.     Design  of  a  High-speed  Steam-engine 8vo,  *5  oo 

—  Physical  Significance  of  Entropy 8vo,  *i  50 

Klingenberg,  G.     Large   Electric   Power  Stations 4to,  *5  oo 

Knight,  R.-Adm.  A.  M.     Modern  Seamanship 8vo,  *6  50 

—  Pocket   Edition ismo,   f abrikoid,  3  oo 

Knott,  C.  G.,  and  Mackay,  J.  S.     Practical  Mathematics 8vo,  2  50 

Knox,  G.  D.    Spirit  of  the  Soil i2mo,  *i  25 

Knox,  J.     Physico-Chemical   Calculations i2mo,  *i  25 

Fixation  of  Atmospheric  Nitrogen.      (Chemical  Monographs.)  .  lamo,  *i  oo 

Koester,  F.     Steam-Electric  Power  Plants 4to,  *5  oo 

— —  Hydroelectric  Developments  and  Engineering 4to,  *5  oo 

Koller,  T.     The  Utilization  of  Waste  Products 8vo,  *6  50 

—  Cosmetics 8vo,  *3  oo 

Koppe,  S.  W.     Glycerine i2mo,  *4  25 

Kozmin,  P.  A.     Flour  Milling.     Trans,  by  M.  Falkner 8vo,  7  50 

Kremann,  R.     Application  of  the  Physico-Chemical  Theory  to  Tech- 
nical  Processes   and   Manufacturing   Methods.     Trans,   by  H. 

E.  Potts 8vo,  *s  oo 

Kretchmar,  K.     Yarn  and  Warp  Sizing ,,,, 8vo,  *6  25 

Laffargue,  A.     Attack  in  Trench  Warfare l6mo,  o  50 

Lallier,  E.  V.    Elementary  Manual  of  the  Steam  Engine i2mo,  *2  oo 

Lambert,  T.     Lead  and  Its   Compounds 8vo,  *4  25 

—  Bone  Products  and  Marurei . ..  . 8vo,  *4  25 

Lamborn,  L.  L.     Cottonseed  Products 8vo,  *3  oo 

—  Modern  Soaps,  Candles,  and  Glycerin 8vo,  *7  50 

Lamprecht,  R.  Recovery  Work  After  Pit  Fires.  Trans,  by  C.  Salter.Svo,  *6  25 

Lancaster,  M.     Electric  Cooking,  Heating  and  Cleaning 8vo,  *i  oo 

Lanchester,  F.  W.    Aerial  Fliglit    Two  Volumes.    8vo. 

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Vol.    II,     Aero^n^t'c,3 ...                                                ...  *6  oo 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG        17 

Lanchester,  F.  W.    The  Flying  Machine 8vo,  *3  oo 

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Lange,  K.  R.    By-Products  of  Coal-Gas  Manufacture i2mo,  3  oo 

Lamer,  E.  T.     Principles  of  Alternating  Currents i2mo.  *i  2* 

La  Rue,  B.  F.     Swing  Bridges.     (Science  Series  No.  107.) i6mo,  o  5  , 

Lassar-Cohn.   Dr.     Modern   Scientific'  Chemistry.     Trans,   by   M.   M. 

Pattison  Muir i2mo,  *2  oo 

Latimer,  L.  H.,  Field,  C.  J.,  and  Howell,  J.  W.  Incandescent  Electric 

Lighting.  (Science  Series  No.  57.)  i6mo,  •  o  50 

Latta,  M.  N.  Handbook  of  American  Gas-Engineering  Practice  .  .  .8vo,  *4  50 

American  Producer  Gas  Practice 410,  *6  oo 

Laws,  B.  C.  Stability  and  Equilibrium  of  Floating  Bodies 8vo,  *3  50 

Lawson,  W.  R.  British  Railways.  A  Financial  and  Commercial 

Survey 8vo,  200 

Leask,  A.  R.  Breakdowns  at  Sea izmo,  2  oo 

Refrigerating  Machinery I2mo,  2  oo 

Lecky,  S.  T.  S.  "Wrinkles"  in  Practical  Navigation 8vo,  10  oo 

—  Pocket    Edition    i2mo,  4  50 

—  Danger    Angle    i6mo,  2  50 

Le  Doux,  M.     Ice-Making  Machines.     (Science  Series  No.  46.) .  .  i6mo,  o  50 

Leeds,  C.  C.    Mechanical  Drawing  for  Trade  Schools oblong  4to,  *2  oo 

Mechanical  Drawing  for  High  and  Vocational  Schools 4to,  *i  25 

Lefevre,  L.     Architectural  Pottery.     Trans,  by  H.  K.  Bird  and  W.  M. 

Binns 4to,  *8  50 

Lehner,  S.    Ink  Manufacture.    Trans,  by  A.  Morris  and  H.  Robson.Svo,  *3  oo 

Lemstrom,  S.     Electricity  in  Agriculture  and  Horticulture 8vo,  *i  50 

Letts,  E.  A.     Fundamental  Problems  in  Chemistry 8vo,  *2  oo 

Le  Van,  W.  B.    Steam-Engine  Indicator.    (Science  Series  No.  78.)i6mo,  o  50 

Lewes,  V.  B.     Liquid  and  Gaseous  Fuels.     (Westminster  Series.) .  .8vo,  *2  oo 

—  Carbonization   of   Coal 8vo,  *5  oo 

Lewis,  L.  P.     Railway  Signal  Engineering 8vo,  *3  50 

Lewis  Automatic  Machine  Rifle  ;  Operation  of i6mo,    *o  75 

Licks,  H.  E.     Recreations  in  Mathematics i2mo,  *i  25 

Lieber,  B.  F.     Lieber*s  Five  Letter  American  Telegraphic  Code  .8vo,  *is  oo 
Spanish   Edition    8vo,  *is  oo 

—  French    Edition    8vo,  *is  oo 

Terminal  Index 8vo,  *2  50 

—  Lieber's  Appendix folio,  "15  oo 

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Bankers  and  Stockbrokers'  Code  and  Merchants  and  Shippers' 

Blank  Tables 8vo,  *i$  oo 

100,000,000  Combination  Code 8vo,  *io  oo 

Engineering  Code 8vo,  "12  50 

Livermore,  V.  P.,  and  Williams,  J.    How  to  Become  a  Competent  Motor- 
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Livingstone,  R.     Design  and  Construction  of  Commutators 8vo,  *2  25 

—  Mechanical  Design  and  Construction  of  Generators 8vo,  *3  50 

Lloyd,   S.   L.     Fertilizer  Materials i2mo,  2  oo 

Lobben,  P.     Machinists'  and  Draftsmen's  Handbook 8vo,  2  50 

Lockwood,  T.  D.     Electricity ;  Magnetism,  and  Electro-telegraph   . .    .8vo,     2  50 
Electrical  Measurement  and  the  Galvanometer i2mo,  o  75 


!8       D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Lodge,  O.  J.  Elementary  Mechanics 12010,  i  50 

Signalling  Across  Space  without  Wires 8vo,  *2  oo 

Loewenstein,  L.  C.,  and  Crissey,  C.  P.     Centrifugal  Pumps *4  50 

Lomax,  J.  W.     Cotton  Spinning 12010,  i  50 

Lord,  R.  T.     Decorative  and  Fancy  Fabrics 8vo,  *4  25 

Loring,  A.  E.     A  Handbook  of  the  Electromagnetic  Telegraph ....  i6mo  o  50 

Handbook.     (Science  Series  No.  39.) i6m,  o  50° 

Lovell,  D.  H.     Practical  Switchwork lamo,  *i  oo 

Low,  D;  A.    Applied  Mechanics  (Elementary) i6mo,  o  80 

Lubsch'es,  B.  J.    Perspective i2mo,  *i  50 

Lucke,  C.  E.     Gas  Engine  Design 8vo,  *3  oo 

Power  Plants:   Design,  Efficiency,  and  Power  Costs.     2  vols. 

(In  Preparation.) 

Luckiesh,  M.     Color  and  Its  Application 8vo,  *3  oo 

—  Light  and  Shade  and  Their  Applications 8vo,  *2  50 

Lunge,  G.    Coal-tar  and  Ammonia.     Three  Volumes 8vo,  *25  oo 

Technical  Gas  Analysis 8vo,  *4  50 

Manufacture  of  Sulphuric  Acid  and  Alkali.    Four  Volumes. . .  .8vo, 

Vol.     I.     Sulphuric  Acid.    In  three  parts *i8  oo 

Vol.  I.    Supplement 8vo,  5  oo 

Vol.  II.     Salt  Cake,  Hydrochloric  Acid  and  Leblanc  Soda.    In  two 

parts (In   Press.) 

Vol.  III.    Ammonia  Soda (In  Press.) 

Vol.  IV.     Electrolytic  Methods (In  Press.) 

Technical  Chemists'  Handbook , i2mo,  leather,  *4  oo 

Technical  Methods  of  Chemical  Analysis.    Trans,  by  C.  A.  Keane 

in  collaboration  with  the  corps  of  specialists. 

Vol.     I.     In  two  parts 8vo,  "15  oo 

Vol.    II.     In  two  parts 8vo,  *i8  oo 

Vol.   III.     In   two   parts 8vo,  *i8  oo 

The  set    (3  vols.)    complete ^50  oo 

Luquer,  L.  M.     Minerals  in  Rock  Sections 8vo,  *i  50 

MacBride,  J.  D.     A  Handbook  of  Practical  Shipbuilding, 

i2mo,  fabrikoid,  2  oo 

Macewen,  H.  A.     Food  Inspection 8vo,  *2  50 

Mackenzie,  N.  F.     Notes  on  Irrigation  Works 8vo,  *2  50 

Mackie,  J.     How  to  Make  a  Woolen  Mill  Pay 8vo,  *2  25 

Maguire,  Wm.  R.    Domestic  Sanitary  Drainage  and  Plumbing  ....  8vo,  4  oo 

Malcolm,  C.  W.    Textbook  on  Graphic  Statics 8vo,    *s  oo 

Malcolm,  R.  W.     Submarine  Telegraph  Cable 8  50 

Mallet,  A.     Compound  Engines.     Trans,  by  R.  R.  Buel.     (Science  Series 

No.  10.) i6mo, 

Mansfield,  A.  N.    Electro-magnets.     (Science  Series  No.  64.)  . .  .  i6mo,  o  50 
Marks,  E.  C.  R.    Construction  of  Cra^e^  end  Lifting  Machinery.  .12010,    *2  oo 

Construction  and  Working  of  Pittrms '.....  i2mo, 

Manufacture  of  Iron  and  Steel  Tubes i2mo,  *2  oo 

—  Mechanical  Engineering  Materials i2mo,    *i  50 

Marks,  G.  C.     Hydraulic  Power  Engineering 8vo,      4  50 

Inventions,  Patents  and  Designs i2mo,  *i  oo 

Marlow,  T.  G.     Drying  Machinery  <md  Practice 8vo,  *5  oo 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG        19 

Marsh,  C.  F.     Concise  Treatise  on  Reinforced  Concrete 8vo,     *2  50 

• Reinforced  Concrete  Compression  Member  Diagram.     Mounted  on 

Cloth  Boards *i .  50 

Marsh,  C.  F.,  and  Dunn,  W.     Manual  of  Reinforced  Concrete  and  Con- 
crete Block  Construction i6mo,  fabrikoid  (In  Press.} 

Marshall,  W.  J.,  and  Sankey,  H.  R.     Gas  Engines.     (Westminster  Series.) 

8vo,     *2  oo 

Martin,  G.     Triumphs  and  Wonders  of  Modern  Chemistry 8vo,       *2  oo 

—  Modern   Chemistry  and  Its  Wonders 8vo,    *2  oo 

Martin,  N.     Properties  and  Design  of  Reinforced  Concrete i2mo,     *2  50 

Martin,  W.  D.    Hints  to  Engineers i2mo,    *i  50 

Massie,  W.  W.,  and  Underbill,  C.  R.     Wireless  Telegraphy  and  Telephony. 

i2mo,     *i  oo 
Mathot,  R.  E.     Internal  Combustion  Engines 8vo,    *4  oo 

Maurice,  W.     Electric  Blasting  Apparatus  and  Explosives 8vo,     *3  50 

• Shot  Firer's  Guide 8vo,     *i  50 

Maxwell,  F.     Sulphitation  in  White  Sugar  Manufacture i2mo,      3  75 

Maxwell,     J.     C.      Matter    and  Motion.       (Science   Series  No.  36.). 

i6mo,    o  50 

Maxwell,  W.  H.,  and  Brown,  J.  T.    Encyclopedia  of  Municipal  and  Sani- 
tary Engineering 4to,  *io  oo 

Mayer,  A.  M.     Lecture  Notes  on  Physics 8vo,     2  oo 


McCullough,  E.     Practical  Surveying i2mo,  *2  oo 

—  Engineering  Work  in  Cities  and  Towns 8vo,  *s  oo 

—  Reinforced  Concrete    i2mo,  *i  50 

McCullough,  R.  S.     Mechanical  Theory  of  Heat 8vo,  3  50 

McGibbon.  W.  C.    Indicator  Diagrams  for  Marine  Engineers 8vo,  :;:3  50 

—  Marine  Engineers'  Drawing  Book oblong  4to,  *2  50 

McGibbon,  W.  C.     Marine  Engineers  Pocketbook i2mo,  *4  50 

Mclntosh,  J.  G.     Technology  of  Sugar 8vo,  *7  25 

—  Industrial  Alcohol    8vo,  *4  25 

Manufacture  of  Varnishes  and  Kindred  Industries.     Three  Volumes. 

8vo. 

Vol.     I.     Oil  Crushing,  Refining  and  Boiling 

Vol.  II.     Varnish  Materials  and  Oil  Varnish  Making...    . *6  25 

Vol.  III.     Spirit  Varnishes  and  Materials *i  25 

McKay,  C.  W.     Fundamental   Principles   of  the  Telephone  Business. 

8vo.    (In  Press.) 

McKillop,  M.,  and  McKillop,  A.  D.     Efficiency  Methods 12 mo,  i  50 

McKnight,  J.  D.,  and  Brown,  A.  W.     Marine  Multitubular  Boilers....  *2  50 
McMaster,  J.  E.     Bridge  and  Tunnel  Centres.     (Science  Series  No.  20.) 

i6mo,  o  50 

McMechen,  F.  L.     Tests  for  Ores,  Minerals  and  Metals i2mo,  *i  oc 

McPherson,  J.  A.     Water-works  Distribution 8vo,  2  50 

Meade,  A.     Modern   Gas   Works   Practice 8vo,  *8  50 

Meade,  R.  K.    Design  and  Equipment  of  Small  Chemical  Laboratories, 

8vo, 

Melick,  C.  W.     Dairy  Laboratory  Guide i2mo,  *i  25 

Mensch,  L.  J.     Reinforced  Concrete  Pocket  Book i6mo,  leather,  *4  oo 

Merck,  E.     Chemical  Reagents;  Their  Purity  and  Tests.     Trans,   by 

H.   E.   Schenck 8vo,  i  oo 

Meriva!e,  J.  H.     Notes  and  Formulae  for  Mining  Students i2mo,  i  50 

Merritt,  Wm.  H.    Field  Testing  for  Gold  and  Silver i6mo,  leather,  2  oo 


20        D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Mertens.     Tactics  and  Technique  of  River  Crossings.     Translated  by 

W.    Kruger 8vo,  2  50 

Mierzinski,  S.     Waterproofing  of  Fabrics.     Trans,  by  A.  Morris  and  H. 

Robson 8 vo,  *3  oo 

Miessner,  B.  F.     Radio  Dynamics xamo,  *2  oo 

Miller,  G.  A.     Determinants.     (Science  Series  No   105.) i6mo, 

Miller,  W.  J.     Introduction  to  Historical  Geology i2mo,  *2  oo 

Milroy,  M.  E.  W.     Home  Lace-making i2mo,  *i  oo 

Mills,  C.  N.    Elementary  Mechanics  for  Engineers 8vo,  *i  oo 

Mitchell,  C.  A.     Mineral  and  Aerated  Waters 8vo,  *3  oo 

Mitchell,  C.  A.,  and  Prideaux,  R.  M.     Fibres  Used  in  Textile  and  Allied 

Industries 8vo,  *3  oo 

Mitchell,  C.  F.,  and  G.  A.     Building  Construction  and  Drawing,     izmo. 

Elementary  Course *i  50 

Advanced  Course *2  50 

Monckton,  C.  C.  F.     Radiotelegraphy.     (Westminster  Series.) 8vo,  *2  oo 

Monteverde,  R.  D.     Vest  Pocket  Glossary  of  English-Spanish,  Spanish- 
English  Technical  Terms 64mo,  leather,  *i  oo 

Montgomery,  J.  H.     Electric  Wiring  Specifications i6mo,  *i  oo 

Moore,  E.  C.  S.     New  Tables  for  the  Complete  Solution  of  Ganguillet  and 

Kutter's  Formula 8vo,  *s  oo 

Moore,  Harold.     Liquid  Fuel  for  Internal  Combustion  Engines.  .  .8vo,  5  oo 
Morecroft,  J.  H.,  and  Hehre,  F.  W.     Short  Course  in  Electrical  Testing. 

8vo,  *i  50 

Morgan,  A.  P.     Wireless  Telegraph  Apparatus  for  Amateurs i2mo,  *i  50 

Morgan,  C.  E.     Practical  Seamanship  for  the  Merchant  Marine, 

i2mo,  fabrikoid  (/;/  Press.) 

Moses,  A.  J.     The  Characters  of  Crystals 8vo,  *2  oo 

—  and  Parsons,  C.  L.     Elements  of  Mineralogy 8vo,  *s  50 

Moss,  S.A.  Elements  of  Gas  Engine  Design. (Science  Series  No.  121. )i6mo,  o  50 

-  The  Lay-out  of  Corliss  Valve  Gears.     (Science  Series  No.  H9.)i6mo,  o  50 

Mulford,  A.  C.     Boundaries  and  Landmarks i2mo,  *i  oo 

Mullin,  J.  P.     Modern  Moulding  and  Pattern-making i2mo,  2  50 

Munby,  A.  E.     Chemistry  and  Physics  of  Building  Materials.     (West- 
minster Series.) 8vo,  *2  oo 

Murphy,  J.  G.     Practical  Mining i6mo,  i  oo 

Murray,  J.  A.     Soils  and  Manures.     (Westminster  Series.) 8vo,  *2  oo 

Nasmith,  J.     The  Student's  Cotton  Spinning 8vo,  4  50 

—  Recent  Cotton  Mill  Construction i2mo,  2  50 

Neave,  G.  B.,  and  Heilbron,  I.  M.     Identification  of  Organic  Compounds. 

i2mo,  *i  25 

Neilson,  R.  M.    Aeroplane  Patents 8vo,  *2  oo 

Nerz,  F.     Searchlights.     Trans,  by  C.  Rodgers 8vo,  *3  oo 

Neuberger,  H.,  and  Noalhat,  H.     Technology  of  Petroleum.     Trans,  by 

J.  G.  Mclntosh 8vo,  *io  oo 

Newall,  J.  W.     Drawing,  Sizing  and  Cutting  Bevel-gears 8vo,  i  50 

Newbigin,  M.  I.,  and  Flett,  J.  S.     James  Geikie,  the  Man  and  the 

Geologist 8vo,  3  50 

Newbeging,  T.     Handbook  for  Gas  Engineers  and  Managers 8vo,  *6  50 

Newell,  F.  H.,  and  Drayer,  C.  E.    Engineering  as  a  Career.  .i2mo,  cloth,  "i  oo 

paper,  o  75 

Nicol,  G.     Ship  Construction  and  Calculations 8vo,  *io  oo 

Nipher,  F.  E.    Theory  of  Magnetic  Measurements ramo,  i  oo 


D.  VAN  NOSTRAXD  CO.'S  SHORT  TITLE  CATALOG  21 

Kisbet,  H.     Grammar  of  Textile  Design 8vo, 

Nolan,  H.     The  Telescope.     (Science  Series  No.  51.) i6mo,  •  50 

Nerie,  J.  W.    Epitome  of  Navigation  (2  Vols.) octavo,  15  oo 

-A  Complete  Set  of  Nautical  Tables  with  Explanations  of  Their 

Use    octavo,  6  50 

North,  H.  B.    Laboratory  Experiments  in  General  Chemistry i2mo,  *i  oo 

Nugent,  E.     Treatise  on  Optics .  I2mo,  i  50 

O'Connor,  H.  The  Gas  Engineer's  Pocketbook lamo,  leather,  3  50 

Olim,  G.  S.,  and  Lockwood,  T.  D.  Galvanic  Circuit  Translated  by 

William  Francis.  (Science  Series  No.  102  , i6mo,  o  50 

Olsen,  J.  C.  Text-book  of  Quantitative  Chemical  Analysis 8vo,  3  50 

Olsson,  A.  Motor  Control,  in  Turret  Turning  and  Gun  Elevating.  (U.  S. 

Navy  Electrical  Series,  No.  i.) i2mo,  paper,  *o  50 

Ormsby,  M.  T.  M.  Surveying i2mo  2  50 

Oudin,  M.  A.  Standard  Polyphase  Apparatus  and  Systems 8vo,  *3  oo 

Owen,  Dr  Recent  Physical  Research 8vo, 

Pakes,  W.  C.  C.,  and  Nankivell,  A.  T.     The  Science  of  Hygiene  .  .8vo,  *i  75 

Palaz,  A.     Industrial  Photometry.     Trans,  by  G.  W.  Patterson,  Jr .  .  8vo,  *4  oo 

Palmer,   A,   R.     Electrical   Experiments i2mo,  o  75 

—  Magnetic  Measurements  and  Experiments i2mo,  o  75 

Pamely,  C.     Colliery  Manager's  Handbook 8vo,  *io  oo 

Parker,  P.  A.  M.     The  Control  of  Water 8vo,  *5  oo 

Parr,  G.  D.  A.     Electrical  Engineering  Measuring  Instruments.  ..  .8vo,  *3  50 
Parry,  E.  J.    Chemistry  of  Essential  Oils  and  Artificial  Perfumes.  ...  10  oo 
Foods  and  Drugs.     Two  Volumes. 

Vol.  I.    Chemical  and  Microscopical  Analysis  of  Foods  and  Drugs.  *xo  oo 

Vol.  II.     Sale  of  Food  and  Drugs  Act *4  25 

and  Coste,  J.  H.    Chemistry  of  Pigments 8vo,  *6  50 

Parry,  L.     Notes  on  Alloys 8vo,  *3  50 

—  Metalliferous   Wastes    8vo,  *2  50 

—  Analysis  of  Ashes  and  Alloys 8vo,  *2  50 

Parry,  L.  A.     Risk  and  Dangers  of  Various  Occupations 8vo,  *4  25 

Parshall,  H.  F.,  and  Hobart,  H.  M.     Armature  Windings    4to,  *7  50 

Electric  Railway  Engineering 4to,  *io  oo 

Parsons,  J.  L.     Land  Drainage 8vo,  *i  50 

Parsons,  S.  J      Malleable  Cast  Iron 8vo,  *2  50 

Partington,  J.  R.    Higher  Mathematics  for  Chemical  Students.  .i2mo,  *2  oo 

—  Textbook  of  Thermodynamics 8vo,  *4  oo 

—  The    Alkali    Industry 8vo,  3  oo 

Passmore,  A.  C.    Technical  Terms  Used  in  Architecture 8vo,  *4  25 

Patchell,  W.  H.     Electric  Power  in  Mines 8vo,  *4  oo 

Paterson,  G.  W.  L.     Wiring  Calculations i2mo,  *3  oo 

—  Electric  Mine  Signalling  Installations i2mo,  *i  50 

Patterson,  D.     The  Color  Printing  of  Carpet  Yarns 8vo,  *4  25 

— — Color   Matching   on   Textiles 8vo,  *4  25 

Textile  Color  Mixing 8vo,  *4  25 

Paulding,  C.  P.     Condensation  of  Steam  in  Covered  and  Bare  Pipes.  .8vo,  *2  oo 

• Transmission  of  Heat  through  Cold-storage  Insulation i2mo,  *i  oo 

Payne,  D.  W.     Iron  Founders'  Handbook 8vo,  *4  oo 

Peckham,  S.  F.     Solid  Bitumens 8vo,  *s  oo 

Peddie,  R.  A.     Engineering  and  Metallurgical  Books i2mo,  *i  50 

Peirce,  B.     System  of  Analytic  Mechanics  410,  10  oo 

—  Linnear   Associative   Algebra 4to,  3  oo 

Pendred,  V.     The  Railway  Locomotive,     (Westminster  Series.) 8vo,  *2  oo 


22        D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Perkin,  F.  M.    Practical  Methods  of  Inorganic  Chemistry i2mo,  *i  oo- 

Perrin,  J.     Atoms 8vo,  *2  50 

and  Jaggers,  E.  M.     Elementary  Chemistry izrno,  *i  oo 

Perrine,  F.  A.  C.     Conductors  for  Electrical  Distribution 8vo,  *3  50 

Petit,  G.    White  Lead  and  Zinc  White  Paints 8vo,  *a  50 

Petit,  R.     How  to  Build  an  Aeroplane.     Trans,  by  T.  O'B.  Hubbard,  and 

J.  H.  Ledeboer 8vo,  *i  50 

Pettit,  Lieut.  J.  S.     Graphic  Processes.     (Science  Series  No.  76.) . . .  i6mo,  o  50 
Philbrick,  P.  H.     Beams  and  Girders.     (Science  Series  No.  88.) . . .  i6mo, 

Phillips,  J.     Gold  Assaying 8vo,  *s  75 

Dangerous  Goods 8vo,  3  50 

Phin,  J.     Seven  Follies  of  Science i2mo,  *i  50 

Pickworth,  C.  N.     The  Indicator  Handbook.     Two  Volumes.  .i2mo,  each,  i  50 

Logarithms  for  Beginners I2mo-  boards,  o  50 

The  Slide  Rule. i2mo,  i  50 

Pilcher,  R.  B.,  and  Butler-Jones,  F.    What  Industry  Owes  to  Chemical 

Science i2mo,  i  50 

Plattner's  Manual  of  Blow-pipe  Analysis.    Eighth  Edition,  revised.    Trans. 

by  H.  B.  Cornwall : 8vo,  *4  oo 

Plympton,  G.  W.    The  Aneroid  Barometer.    (Science  Series  No.  35.)   i6mo,  o  50' 

How  to  become  an  Engineer.     (Science  Series  No.  100.) i6mo,  o  50 

Van  Nostrand's  Table  Book.     (Science  Series  No.  104.) i6mo,  o  50 

Pochet,  M.  L.     Steam  Injectors.     Translated  from  the  French.     (Science 

Series  No.  29.) > .  , .  i6mo,  o  50 

Pocket  Logarithms  to  Four  Places.     (Science  Series  No.  65.) i6mo,  o  50 

leather,  i  oo 

Polleyn,  F.     Dressings  and  Finishings  for  Textile  Fabrics 8vo,  *3  oo 

Pope,  F.  G.    Organic  Chemistry xaxn'o,  2  50 

Pope,  F.  L.     Modern  Practice  of  the  Electric  Telegraph 8vo,  i  50 

Popplewell,  W.  C.     Prevention  of  Smoke 8vo,  *4  25 

—  Strength   of   Materials 8vo,  *2  50 

Porritt,  B.   D.     The   Chemistry   of   Rubber.      (Chemical   Monographs, 

No.  3.) i2mo,  *i  oa 

Porter,  J.  R.    Helicopter  Flying  Machine .......  i2mo,  i  50 

Potts,  H.  E.     Chemistry  of  the  Rubber  Industry.     (Outlines  of  Indus- 
trial  Chemistry) 8vo,  *2  so- 
Practical   Compounding  cf  Oils,  Tallow  and   Grease 8vo,  *4  25 

Pratt,  K.     Boiler  Draught i2mo,  *i  25 

High  Speed  Steam   Engines 8vo,  *2  oo 

Pray,  T.,  Jr.     Twenty  Years  with  the  Indicator 8vo,  2  50 

Steam  Tables  and  Engine  Constant 8vo,  2  oo 

Prelim,  C.     Earth  and  Rock  Excavation 8vo,  *3  oo 

Graphical  Determination  of  Earth  Slopes 8vo,  *2  oo 

Tunneling.     New  EditioD 8vo,  *3  oo 

Dredging.    A  Practical  Treatise 8vo,  *3  oo 

Prescott,  A.  B.     Organic  Analysis 8vo,  5  oo 

Prescott,  A.  B.,  and  Johnson,  O.  C,     Qualitative  Chemical  Analysis.  .  .8vo,  *3  50 
Prescott,  A.  B.,  and  Sullivan,  E.  C.     First  Book  in  Qualitative  Chemistry. 

i2mo,  *i  50 

Prideaux,  E.  B.  R.     Problems  in  Physical  Chemistry 8vo,  *2  oo 

—  The  Theory  and  Use  of  Indicators 8vo,  5  oo 

Primrose,  G.  S.  C.     Zinc.     (Metallurgy  Series.) (In  Press.} 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  23 

Prince,  G.  T.    Flow  of  Water i2mo,  *2  oo 

Pull,  E.     Modern  Steam  Boilers 8vo,  5  oo 

Pullen,  W.  W.   F.     Application  of  Graphic  Methods  to  the  Design  of 

Structures i2mo,  *2  50 

—  Injectors:    Theory,   Construction   and  Working i2mo,  *2  oo 

— Indicator   Diagrams    8vo,  *2  50 

—  Engine  Testing   8vo,  *5  50 

Putsch,  A.     Gas  and  Coal-dust  Firing 8vo,  *3  oo 

Pynchon,  T.  R.     Introduction  to  Chemical  Physics 8vo,  3  oo 

Rafter  G.  W      Mechanics  of  Ventilation.     (Science  Series  No.  33.) .  i6mo,  o  50 
Potable  Water.     (Science  Series  No.  103.) i6mo,  o  50 

—  Treatment  of  Septic  Sewage.     (Science  Series  No.  118.) .  . .  i6mo,  o  50 
Rafter,  G.  W.,  and  Baker,  M.  N.     Sewage  Disposal  in  the  United  States. 

410,  *6  oo 

Raikes,  H.  P.     Sewage  Disposal  Works 8vo,  *4  oo 

Randau,  P.  Enamels  and  Enamelling 8vo,  *y  25 

Rankine,  W.  J.  M.     Applied  Mechanics 8vo,  5  oo 

—  Civil  Engineering 8vo,  6  50 

-  Machinery  and  Millwork 8vo,  5  oo 

The  Steam-engine  and  Other  Prime  Movers 8vo,  5  oo 

Rankine,  W.  J.  M.,  and  Bamber,  E.  F.     A  Mechanical  Text-book 8vo,  3  50 

Ransome,  W.  R.    Freshman  Mathematics i2mo,  *i  35 

Raphael,  F.  C.     Localization  of  Faults  in  Electric  Light  and  Power  Mains. 

8vo,  3  50 

Rasch,  E.    Electric  Arc  Phenomena.    Trans,  by  K.  Tornberg 8vo,  *2  oo 

Rathbone,  R.  L.  B.     Simple  Jewellery 8vo,  *2  oo 

Rateau,  A.     Flow  of  Steam  through  Nozzles  and  Orifices.     Trans,  by  H. 

B.  Brydon 8vo  *i  50 

Rausenberger,  F.     The  Theory  of  the  Recoil  Guns 8vo,  *s  oo 

Rautenstrauch,  W.    Notes  on  the  Elements  of  Machine  Design. 8 vo,  boards,  *i  50 
Rautenstrauch,  W.,  and  Williams,  J.  T.     Machine  Drafting  and  Empirical 

Design. 

Part   I.  Machine  Drafting 8vo,  *i  25 

Part  II.  Empirical  Design (In  Preparation.) 

Raymond,  E.  B.     Alternating  Current  Engineering i2mo,  *2  50 

Rayner,  H.     Silk  Throwing  and  Waste  Silk  Spinning 8vo, 

Recipes  for  the  Color,  Paint,  Varnish,  Oil,  Soap  and  Drysaltery  Trades, 

8vo,  *6  50 

Recipes  for  Flint  Glass  Making 12010,  *s  25 

Redfern,  J.  B.,  and  Savin,  J.    Bells,  Telephones  (Installation  Manuals 

Series.) i6mo,  *o  50 

Redgrove,  H.  S.     Experimental  Mensuration i2mo,  *i  25 

Redwood,  B.     Petroleum.     (Science  Series  No.  92.) i6mo,  o  50 

Reed,  S.    Turbines  Applied  to  Marine  Propulsion *5  oo 

Reed's  Engineers'  Handbook 8vo,  *g  oo 

Key  to  the  Nineteenth  Edition  of  Reed's  Engineers'  Handbook.  .8vo,  4  oo 

—  Useful  Hints  to  Sea-going  Engineers i2mo,  3  oo 

Reid,  E.  E.    Introduction  to  Research  in  Organic  Chemistry.  (In  Press.) 

Reid,  H.  A.     Concrete  and  Reinforced  Concrete  CoDstruction 8vo,  *s  oo 

Reinhardt,  C  W.     Lettering  for  Draftsmen,  Engineers,  and  Students. 

oblong  4to,  boards,  i  oo 


24       B.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Reinhardt,  C.  W.   The  Technic  of  Mechanical  Drafting, 

oblong,  4to,  boards,  *i  oo 
Reiser,  F.     Hardening  and  Tempering  of  Steel.     Trans,  by  A.  Morris  and 

H.    Robson    iamo,  *3  oo 

Reiser,  N.     Faults  in  the  Manufacture  of  Woolen  Goods.     Trans,  by  A. 

Morris  and  H.  Robson 8vo,  *3  oo 

—  Spinning   and  Weaving  Calculations. 8vo,  *6  25 

Renwick,  W.  G.     Marble  and  Marble  Working 8vo,  5  oo 

Reuleaux,  F.     The  Constructor.     Trans,  by  H.  H.  Suplee 4to,  *4  oo 

Reuterdahl,  A.    Theory  and  Design  of  Reinforced  Concrete  Arches. 8vo,  *2  oo 

Rey,  Jean.     The  Range  of  Electric  Searchlight  Projectors 8vo,  */  50 

Reynolds,   0.,   and   Idell,    F.   E.     Triple   Expansion   Engines.     (Science 

Series  No.  99.)         i6mo,  o  50 

Rhead,  G.  F.     Simple  Structural  Woodwork i2mo,  *i  25 

Rhodes,  H.  J.     Art  of  Lithography 8vo,  6  50 

Rice,  J.  M.,  and  Johnson,  W.  W.     A  New  Method  of  Obtaining  the  Differ- 
ential of  Functions i2mo,  o  50 

Richards,  W.  A.     Forging  of  Iron  and  Steel i2mo,  i  50 

Richards,  W.  A.,  and  North,  H.  B.    Manual  of  Cement  Testing. .  .  .  i2mo,  *i  50 

Richardson,  J.     The  Modern  Steam  Engine 8vo,  *3  50 

Richardson,  S.  S.     Magnetism  and  Electricity i2mo,  *2  oo 

Rideal,  S.    Glue  and  Glue  Testing 8vo,  *6  50 

Riesenberg,  F.     The  Men  on  Deck .  i2tno,  3  oo 

—  Standard  Seamanship  for  the  Merchant  Marine.  i2mo  (In  Press.) 

Rimmer,  E.  J.    Boiler  Explosions,  Collapses  and  Mishaps 8vo,  *i  75 

Rings,  F.     Reinforced  Concrete  in  Theory  and  Practice i2mo,  *4  50 

Reinforced  Concrete  Bridges 410,  *$  oo 

Ripper,  W.     Course  of  Instruction  in  Machine  Drawing folio,  *6  oo 

Roberts,  F.  C.     Figure  of  the  Earth.     (Science  Series  No.  79.) i6mo,  o  50 

Roberts,  J.,  Jr.     Laboratory  Work  in  Electrical  Engineering   8vo,  *2  oo 

Robertson,  L.  S.     Water-tube  Boilers 8vo,  2  oo 

Robinson,  J.  B.     Architectural  Composition 8vo,  *2  50 

Robinson,  S.  W.     Practical  Treatise  on  the  Teeth  of  Wheels.     (Science 

Series  No.  24.) i6mo,  o  50. 

—  —  Railroad  Economics.     (Science  Series  No.  59.) i6mo,  o  50 

Wrought  Iron  Bridge  Members.     (Science  Series  No.  60.) i6mo,  o  50 

Robson,  J.  H.     Machine  Drawing  and  Sketching 8vo,  *2  oo 

Roebling,  J.  A.     Long  and  Short  Span  Railway  Bridges folio,  25  oo 

Rogers,  A.     A  Laboratory  Guide  of  Industrial  Chemistry 8vx),  2  oo 

. Elements    of    Industrial    Chemistry i2mo,  *3  oo 

—  Manual  of  Industrial  Chemistry 8vo,  *s  oo 

Rogers,  F.     Magnetism  of  Iron  Vessels.     (Science  Series  No.  30.).  i6mo,  o  So 
Rohland,  P.     Colloidal  and  Crystalloidal  State  of  Matter.     Trans,  by 

W.  J.  Britland  and  H.  E.  Potts i2mo,  *i  25 

Rollinson,  C.     Alphabets Oblong,  i2mo,  *i  oo 

Rose,  J.     The  Pattern-makers'  Assistant 8vo,  2  50 

— -  Key  to  Engines  and  Engine -running i2mo,  2  50 

Rose,  T.  K.     The  Precious  Melals.     (Westminster  Series.) 8vo,  *2  oo 

Rosenhain,  W.     Glass  Manufacture.     (Westminster  Series.) 8vo,  *2  oo 

—  Physical  Metallurgy,  An  Introduction  to.      (Metallurgy  Series.) 

8vo,  *3  50 

Roth,    W.    A.     Physical    Chemistry 8vo,  *2  oo 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  25 

Rowan,  F.  J.    Practical  Physics  of  the  Modern  Steam-boiler 8vo,  *3  oo 

and    Idell,   F.    E.     Boiler   Incrustation   and   Corrosion.      (Science 

Series  No.  27.) i6mo,  o  50 

Roxburgh,  W.    General  Foundry  Practice.     (Westminster  Series.)  .8vo,  *2  oo 

Ruhmer,  E.    Wireless  Telephony.     Trans,  by  J.  Erskine-Murray.  .8vo,  *4  50 

Russell,  A.     Theory  of  Electric  Cables  and  Networks 8vo,  *3  oo 

Rust,  A.     Practical  Tables  for  Navigators  and  Aviators 8vo,  3  50 

Rutley,  F.     Elements  of  Mineralogy i2mo,  *i  25 

Sandeman,  E.  A.    Notes  on  the  Manufacture  of  Earthenware.  .  .xamo,  3  50 

Sanford,  P.  G.     Nitro-explosives 8vo,  *4  oo 

Saunders,  C.  H.     Handbook  of  Practical  Mechanics i6mo,  i  oo 

leather,  i  25 

Sayers,  H.  M.     Brakes  for  Tram  Cars 8vo,  *i  25 

Scheele,  C.  W.     Chemical  Essays 8vo,  *2  oo 

Scheithauer,  W.     Shale  Oils  and  Tars 8vo,  *5  oo 

Scherer,  R.     Casein.     Trans,  by  C.  Salter 8vo,  *4  25 

Schidrowitz,  P.    Rubber,  Its  Production  and  Industrial  Uses SVG,  ^6  oo 

Schindler,  K.     Iron  and  Steel  Construction  Works i2mo,  *2  25 

Schmall,  C.  N.     First  Course  in  Analytic  Geometry,  Plane  and  Solid. 

i2mo,  half  leather,  *i  75 

Schmeer,  L.     Flow  of  Water 8vo,  *3  oo 

Schumann,  F.    A  Manual  of  Heating  and  Ventilation.  ..  .i2mo,  leather,  i  50 

Schwarz,  E.  H.  L.     Causal  Geology 8vo,  *3  oo 

Schweizer,  V.     Distillation  of  Resins 8vo,  4  50 

Scott,   W.   W.     Qualitative   Analysis.     A  Laboratory  Manual.     New 

Edition 2  50 

Standard   Methods    of   Chemical    Analysis 8vo,  *6  oo 

Scribner,  J.  M.    Engineers'  and  Mechanics'  Companion.  .i6mo,  leather,  i  50 
Scudder,    H.      Electrical    Conductivity    and    lonization    Constants    of 

Organic  Compounds 8vo,  *3  oo 

Seamanship,  Lectures  on i2mo    (In   Press.) 

Searle,   A.    B.     Modern    Brickmaking 8vo,  *j  25 

Cement,  Concrete  and  Bricks 8vo,  *6  50 

Searle,     G.     M.       "Sumners'     Method."      Condensed     and     Improved. 

(Science  Series  No.    124.) i6mo,  o  50 

Seaton,  A.  E.     Manual  of  Marine  Engineering 8vo  8  oo 

Seaton,  A.  E.,  and  Rounthwaite,  H.  M.     Pocket-book  of  Marine  Engi- 
neering  i6mo,  leather,  5  oo 

SeeJigmann,  T.,  Torrilhon,  G.  L.,  and  Falconnet,  H.    India  Rubber  and 

Gutta  Percha.     Trans,  by  J.  G.  Mclntosh 8vo,  *5  oo 

Seidell,  A.     Solubilities  of  Inorganic  and  Organic  Substances ....  8vo,  3  oo 

Seligman,   R.     Aluminum.      (Metallurgy   Series.) (In  Press.) 

Sellew,  W.   H.     Steel   Rails 4to,  *io  oo 

Railway    Maintenance    Engineering i2tno,  *2  50 

Senter,  G.     Outlines  of  Physical  Chemistry i2mo,  *2  oo 

Text-book  of  Inorganic  Chemistry i2mo,  *3  oo 

Sever,  G.  F.    Electric  Engineering  Experiments 8vo,  boards,  *i  oo 

Sever,  G.  F.,  and  Townsend,  F.    Laboratory  and  Factory  Tests  in  Elec- 
trical Engineering 8vo,  *2  50 

Sewall,  C.  H.    Wireless  Telegraphy 8vo,  *2  oo 

Lessons  in  Telegraphy i2mo,  *i  oo 


26       D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Sewell,  T.     The  Construction  of  Dynamos 8vo,  *3  oo 

Sexton,  A.  H.     Fuel  and  Refractory  Materials i2mo,  *2  50 

—  Chemistry  of  the  Materials  of  Engineering i2mo,  *a  50 

—  Alloys   (Non-Ferrous) 8vo,  *3  oo 

Sexton,  A.  H.,  and  Primrose,  J.  S.  G.  The  Metallurgy  of  Iron  and  Steel. 

8vo,  *6  50 

Seymour,  A.     Modern  Printing  Inks 8vo,  *3  oo 

Shaw,  Henry  S.  H.    Mechanical  Integrators.    (Science  Series  No.  83.) 

i6mo,  o  50 

Shaw,  S.    History  of  the  Staffordshire  Potteries 8vo,  3  oo 

—  Chemistry  of  Compounds  Used  in  Porcelain  Manuf acture .  . .  .  8vo,  *6  oo 
Shaw,    T.  R.     Driving  of  Machine  Tools i2mo,  *2  50 

—  Precision    Grinding    Machines 1210.0,  4  50 

Shaw.  W.  N.     Forecasting   Weather 8vo,  *3  50 

Sheldon,  S.,  and  Hausmann,  E.    Direct  Current  Machines i2mo,  *2  50 

Alternating  Current  Machines i2mo,  *2  50 

Sheldon,  S.,  and  Hausmann,  E.     Electric  Traction  and  Transmission 

Engineering i2mo,  *2  50 

Physical  Laboratory  Experiments,  for  Engineering  Students.  .8vo,  *i  25 

Shields,  J.  E.     Notes  on  Engineering  Construction i2mo,  i  50 

Shreve,  S.  H.     Strength  of  Bridges  and  Roofs 8vo,  3  50 

Shunk,  W.  F.    The  Field  Engineer i2mo,  fabrikoid,  2  50 

Simmons,  W.  H.,  and  Appleton,  H.  A.    Handbook  of  Soap  Manufacture, 

8vo,  *5  oo 

Simmons,  W.  H.,  and  Mitchell,  C.  A.     Edible  Fats  and  Oils 8vo,  *4  50 

Simpson,  G.     The  Naval  Constructor i2mo,  fabrikoid,  *s  oo 

Simpson,  W.     Foundations 8vo.    (In  Press.) 

Sinclair,  A.     Development  of  the  Locomotive  Engine. .  .8vo,  half  leather,  5  oo 

Sindall,  R.  W.    Manufacture  of  Paper.     (Westminster  Series.) 8vo,  *2  oo 

Sindall,  R.  W.,  and  Bacon,  W.  N.     The  Testing  of  Wood  Pulp 8vo,  *2  50 

Sloane,  T.  O'C.     Elementary  Electrical  Calculations i2mo,  *2  oo 

Smallwood,  J.  C.     Mechanical  Laboratory  Methods.     (Van  Nostrand's 

Textbooks.)    i2mo,  fabrikoid,  *3  oo 

Smith,  C.  A.  M.     Handbook  of  Testing,  MATERIALS 8vo,  *2  50 

Smith,  C.  A.  M.,  and  Warren,  A.  G.     New  Steam  Tables 8vo,  *i  25 

Smith,  C.  F.     Practical  Alternating  Currents  and  Testing 8vo,  *3  50 

—  Practical    Testing    of    Dynamos    and    Motors 8vo,  *3  oo 

Smith,  F.   A.     Railway   Curves i2mo,  *i  oo 

Standard    Turnou  ts    on   Americ  an    Railroads i2mo,  *i  oo 

Maintenance    of   Way   Standards i2mo,  *i  50 

Smith,  F.  E.     Handbook  of  General  Instruction  for  Mechanics.  .  .i2mo,  i  50 
Smith,  G.  C.     Trinitrotoluenes  and  Mono-  and  Dinitrotoluenes,  Their 

Manufacture  and   Properties i2mo,  2  oo 

Smith,  H.  G.    Minerals  and  the  Microscope i2mo,  *i  25 

Smith,  J.  C.     Manufacture  of  Paint 8vo,  *3  50 

Smith,  R.  H.     Principles  of  Machine  Work , i2mo, 

—  Advanced  Machine  Work i2mo,  *3  oo 

Smith,  W.     Chemistry  of  Hat  Manufacturing i2mo,  *4  50 

Snell,    A.    T.     Electric    Motive  Power 8vo,  *4  oo 

Snow,  W.  G.     Pocketbook  of  Steam  Heating  and  Ventilation.    (In  Press.) 
Snow,  W.  G.,  and  Nolan,  T.     Ventilation  of  Buildings.     (Science  Series 

No.  5.) i6mo,  o  50 

Soddy,  F.     Radioactivity 8vo,  *3  oo 


D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG  27 

Solomon,  M.     Electric  Lamps.     (Westminster  Series.) 8vo,  *2  oo 

Somerscales,  A.  N.     Mechanics  for  Marine  Engineers 1210.0,  *2  oo 

—  Mechanical  and  Marine  Engineering  Science 8vo,  *s  oo 

Sothern,  J.  W.     The  Marine   Steam  Turbine 8vo,  *i$  oo 

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Sothern,   J.    W.,   and    Sothern,   R.    M.     Elementary   Mathematics    for 

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Southcombe,  J.  E.     Chemistry  of  the  Oil  Industries.     (Outlines  of  In- 
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Soxhlet,  D.  H.     Dyeing  and  Staining  Marble.     Trans,  by  A.  Morris  and 

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Spangenburg,  L.  Fatigue  of  Metals.  Translated  by  S.  H.  Shreve. 

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Spencer,  A.  S.  Design  of  Steel-Framed  Sheds 8vo,  *3  50 

Speyers,  C.  L.  Text-book  of  Physical  Chemistry 8vo,  *i  50 

Spiegel,  L.  Chemical  Constitution  and  Physiological  Action.  (  Trans. 

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Sprague,  E.  H.  Hydraulics i2mo,  150 

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Stahl,  A.  W.     Transmission  of  Power.     (Science  Series  No.  28.)  .  i6mo, 

Stahl,  A.  W.,  and  Woods,  A.  T.     Elementary  Mechanism i2mo,  *2  oo 

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Stanley,  H.    Practical  Applied  Physics (In  Press.) 

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Steadman,  F.  M.     Unit  Photography i2mo,  *2  oo 

Stecher,  G.  E.     Cork.    Its  Origin  and  Industrial  Uses i2mo,  i  oo 

Steinheil,   A.,   and   Voit,   E.     Applied   Optics 8vo,  500 

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Stevens,  E.  J.     Field  Telephones  and  Telegraphs i  20 

Stevens,  H.  P.     Paper  Mill  Chemist  iomo,  *4  25 

Stevens,  J.  S.     Theory  of  Measurements i2mo,  *x  25 

Stevenson,  J.  L.     Blast-Furnace  Calculations 12010,  leather,  *2  oo 

Stewart,  G.    Modern  Steam  Traps i2mo,  *i  75 

Stiles,  A.     Tables  for  Field  Engineers i2mo,  i  oo 

Stodola,  A.    Steam  Turbines.    Trans,  by  L.  C.  Loewenstein 8vo,  *5  oo 

Stone,  H.    The  Timbers  of  Commerce 8vo,  3  50 

Stopes,  M.     Ancient  Plants 8vo,  *2  oo 

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Sudborough,  J.  J.,  and  James,  T.  C.    Practical  Organic  Chemistry.  12010,  *2  oo 

Suf fling,  E.  R.     Treatise  on  the  Art  of  Glass  Painting 8vo,  *4  25 

Sullivan,  T.  V.,  and  Underwood,  N.     Testing  and  Valuation  of  Build- 
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28        D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

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Svenson,  C.  L.     Handbook  on  Piping 8vo,  4  oo- 

Essentials  of  Drafting 8vo,  i  50 

Swan,  K.     Patents,  Designs  and  Trade  Marks.     (Westminster  Series.). 

8vo,  *2  oo 
Swinburne,  J.,  Wordingham,  C.  H.,  and  Martin,  T.  C.     Electric  Currents. 

(Science  Series  No.  109.) i6mo,  o  50 

Swoope,  C.  W.     Lessons  in  Practical  Electricity i2mo,  *2  oo 

Tailfer,  L.     Bleaching  Linen  and  Cotton  Yarn  and  Fabrics 8vo,  8  50 

Tate,  J.  S.     Surcharged  and  Different  Forms  of  Retaining-walls.    (Science 

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Taylor,  F.  N.     Small  Water  Supplies i2mo,  *2  50 

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Taylor,   W.   P.     Practical   Cement   Testing 8vo,  *s  oo 

Templeton,  W.     Practical  Mechanic's  Workshop  Companion. 

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Terry,  H.L.    India  Rubber  and  its  Manufacture.     (Westminster  Series.) 

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Thayer,  H.  R.     Structural  Design.     8vo. 

Vol.     I.    Elements  of  Structural  Design *2  oo 

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Thiess,  J.  B.,  and  Joy,  G.  A.     Toll  Telephone  Practice 8vo,  *3  50 

Thorn,  C.,  and  Jones,  W.  H.     Telegraphic  Connections.. .  .oblong,  i2mo,  150 

Thomas,  C.  W.     Paper-makers'  Handbook (In  Press.) 

Thomas,  J.  B.     Strength  of  Ships 8vo,  3  oo 

Thomas,  Robt.  G.     Applied  Calculus i2mo   (In  Press.) 

Thompson,  A.  B.     Oil  Fields  of  Russia 4to,  *7  50 

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Thompson,  S.  P.     Dynamo  Electric  Machines.     (Science  Series  No.  75.) 

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Thompson,  W.  P.     Handbook  of  Patent  Law  of  All  Countries i6rno,  i  50 

Thomson,  G.    Modern  Sanitary  Engineering i2mo,  *s  oo 

Thomson,  G.  S.     Milk  and  Cream   Testing 12010,  *2  25 

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Todd,  J.,  and  Whall,  W.  B.     Practical  Seamanship 8vo,  8  oo 

Tonge,  J.     Coal.     (Westminster  Series.) 8vo,  *2  oo 

Townsend,  F.     Alternating  Current  Engineering 8vo,  boards,  *o  75 

Townsend,  J.  S.     lonization  of  Gases  by  Collision 8vo,  *i  25 

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Treiber,  E.    Foundry  Machinery.    Trans,  by  C.  Salter i2mo,  i  50 

Trinks,  W.,  and  Housum,  C.     Shaft  Governors.     (Science  Series  No.  122.) 

i6mo,  o  50 

Trowbridge,  W.  P.     Turbine  Wheels.     (Science  Series  No.  44.) .  .  i6mo,  o  50 

Tucker,  J.  H.     A  Manual  of  Sugar  Analysis 8vo,  3  50 

Tunner,  P.  A.     Treatise  on  Roll-turning.     Trans,  by  J.  B.  Pearse. 

8vo,  text  and  folio  atlas,  10  oo 
Turnbull,  Jr.,  J.,  and  Robinson,  S.  W.     A  Treatise  on  the  Compound 

Steam-engine.     (Science  Series  No.  8.) i6mo, 

Turner,  H.     Worsted  Spinners'  Handbook i2mo,  *s  50 

Turrill,  S.  M.     Elementary  Course  in  Perspective i2mo,  *i  25 

Twyford,   H.   B.     Purchasing 8vo,  *3  oo 

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Tyrrell,  H.  G.     Design  and  Construction  of  Mill  Buildings 8vo,  *4  oo 

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Underbill,  C.  R.     Solenoids,  Electromagnets  and  Electromagnetic  Wind- 
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Underwood,   N.,  and  Sullivan,  T.  V.     Chemistry   and   Technology   of 

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Urquhart,  J.  W.     Electro-plating lamo,  2  oo 

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Usborne,  P.  O.  G.     Design  of  Simple  Steel  Bridges 8vo,  *4  oo 

Vacher,  F.    Food  Inspector's  Handbook i2mo, 

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Van  Wagenen,  T.  F.     Manual  of  Hydraulic  Mining i6mo,  i  oo 

Vega,   Baron   Von.     Logarithmic  Tables 8vo,  2  50 

Vincent,  C.    Ammonia  and  its  Compounds.    Trans,  by  M.  J.  Salter. 8vo,  *3.  oo 

Volk,  C.     Haulage  and  Winding  Appliances 8vo,  *4  oo 

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Vose,  G.  L.     Graphic  Method  for  Solving  Certain  Questions  in  Arithmetic 

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30        D.  VAN  NOSTRAND  CO.'S  SHORT  TITLE  CATALOG 

Vosmaer,  A.     Ozone 8vo,  *2  50 

Wabner,  R.     Ventilation  in  Mines.     Trans,  by  C.  Salter 8vo,  *6  50 

Wade,  E.  J.     Secondary  Batteries 8vo,  *4  o° 

Wadmore,  T.  M.     Elementary  Chemical  Theory i2mo,  *i  50 

Wagner,   E.     Preserving   Fruits,   Vegetables,   and   Meat... 12010,  *3  oo 

Wagner,  J.  B.     A  Treatise  on  the  Natural  and  Artificial  Processes  of 

Wood    Seasoning 8vo,  3  oo 

Waldram,  P.  J.     Principles  of  Structural  Mechanics i2mo,  *3  oo 

Walker,  F.    Dynamo  Building.     (Science  Series  No.  98.) i6mo,  o  50 

Walker,  J.     Organic  Chemistry  for  Students  of  Medicine 8vo,  *3  oo 

Walker,  S.  F.     Steam  Boilers,  Engines  and  Turbines 8vo,  3  oo 

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— • —  Electricity  in  Mining 8vo,  *4  50 

Wallis-Tayler,  A.  J.     Bearings  and  Lubrication 8vo,  *i  50 

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—  Preservation  of  Wood 8vo,  4  oo 

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Walsh,  J.  J.    Chemistry  and  Physics  of  Mining  and  Mine  Ventilation, 

i2mo,  *2  oo 

Wanklyn,  J.  A.    Water  Analysis i2mo,  2  oo 

Wansbrough,  W.  D.    The  A  B  C  of  the  Differential  Calculus. ..  .i2mo,  *2  50 

—  Slide  Valves i2mo,  *2  oo 

Waring,  Jr.,  G.  E.    Sanitary  Conditions.    (Science  Series  No.  31.) .  i6mo,  o  50 

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Modern  Methods  of  Sewage  Disposal i2mo,  2  oo 

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Warnes,  A.  R.     Coal  Tar  Distillation 8vo,  *s  bo 

Warren,  F.  D.    Handbook  on  Reinforced  Concrete i2mo,  *2  50 

Watkins,  A.     Photography.     (Westminster  Series.) 8vo,  *2  oo 

Watson,  E.  P.    Small  Engines  and  Boilers i2mo,  i  25 

Watt,  A.     Electro-plating  and  Electro-refining  of  Metals 8vo,  *4  50 

Electro -metallurgy i2mo,  i  oo 

The  Art  of  Soap  Making '. 8vo,  3  oo 

Leather  Manufacture 8vo,  *4  oo 

Paper-Making 8vo,  3  oo 

Webb,  H.  L.   Guide  to  the  Testing  of  Insulated  Wires  and  Cables.  i2mo,  i  oo 

Webber,  W.  H.  Y.    Town  Gas.     (Westminster  Series.) .8vo,  *2  oo 

Wegmann,    Edward.      Conveyance    and    Distribution    of    Water    for 

Water  Supply 8vo,  5  oo 

Weisbach,  J.    A  Manual  of  Theoretical  Mechanics 8vo,  *6  oo 

sheep,  *7  50 

Weisbach,  J.,  and  Herrmann,  G.     Mechanics  of  Air  Machinery ....  8vo,  *3  75 

Wells,   M.   B.     Steel   Bridge   Designing 8vo,  *2  50 

Wells,  Robt.     Ornamental   Confectionery i2mo,  3  oo 

Weston,  E.  B.    Loss  of  Head  Due  to  Friction  of  Water  in  Pipes.  .12010,  *i  50 

Wheatley,  0.     Ornamental  Cement  Work 8vo,  *2  25 

Whipple,  S.    An  Elementary  and  Practical  Treatise  on  Bridge  Building. 

8vo,  3  oo 
White,  C.  H.     Methods  of  Metallurgical  Analysis.     (Van  Nostrand's 

Textbooks.)     i2mo,  2  50 


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White,  G.  F.    Qualitative  Chemical  Analysis i2mo,  *i  25 

White,  G.  T.     Toothed  Gearing i2mo,  *2  25 

White,  H.  J.     Oil  Tank  Steamers i2mo,  i  50 

Whitelaw,    John.      Surveying 8vo,  4  50 

Widmer,  E.  J.     Military   Balloons 8vo,  3  oo 

Wilcox,  R.  M.      Cantilever  Bridges.     (Science  Series  No.  25.) i6mo,  o  50 

Wilda,  H.     Steam  Turbines.     Trans,  by  C.  Salter i2mo,  2  50 

—  Cranes  and  Hoists.     Trans,   by  C.  Salter i2mo,  2  50 

Wilkinson,  H.  D.     Submarine  Cable   Laying  and  Repairing 8vo,  *6  oo 

Williamson,   J.     Surveying 8vo,  *3  oo 

Williamson,  R.  S.     On  the  Use  of  the  Barometer 4to,  15  oo 

—  Practical  Tables  in  Meteorology  and  Hypsometery 4to,  2  50 

Wilson,  F.  J.,  and  Heilbron,  I.  M.     Chemical  Theory  and  Calculations. 

i2mo,  "i  25 

Wilson,  J.  F.     Essentials  of  Electrical  Engineering 8vo,  2  50 

Wirnperis,  H.  E.     Internal  Combustion  Engine 8vo,  *3  oo 

—  Application  of  Power  to  Road  Transport i2mo,  *i  50 

—  Primer  of  Internal  Combustion  Engine i2mo,  *i  oo 

Winchell,  N.  H.,  and  A.  N.     Elements  of  Optical  Mineralogy 8vo,  *3  50 

Wmslow,  A.    Stadia  Surveying.     (Science  Series  No.  77.) i6mo,  o  50 

Wisser,  Lieut.  J.  P.     Explosive  Materials.     (Science  Series  No.  70.) 

i6mo,  o  50 

Wisser,  Lieut.  J.  P.  Modern  Gun  Cotton.  (Science  Series  No.  89.)  .i6mo,  o  50 

Wolff,  C.  E.  Modern  Locomotive  Practice 8vo,  *4  20 

Wood,  De  V.  Luminiferous  Aether.  (Science  Series  No.  8s)...i6mo,  o  50 
Wood,  J.  K.  Chemistry  of  Dyeing.  (Chemical  Monographs  No.  2.) 

i2mo,  *i  oo 

Worden,  E.  C.  The  Nitrocellulose  Industry.  Two  Volumes 8vo,  *io  oo 

—  Technology  of  Cellulose  Esters.     In  10  volumes.    8vo. 

Vol.  VIII.     Cellulose  Acetate *5  oo 

Wren,  H.    Organometallic  Compounds  of  Zinc  and  Magnesium.    (Chem- 
ical   Monographs    No.    i.) i2ino,  *i  oo 

Wright,  A.  C.     Analysis  of'  Oils  and  Allied  Substances 8vo,  *3  50 

—  Simple  Method  for  Testing  Painters'  Materials 8vo,  *3  oo 

Wright,  F.  W.     Design  of  a   Condensing  Plant i2mo,  *i  50 

Wright,  H.  E.     Handy  Book  for  Brewers 8vo,  *6  oo 

Wright,  J.     Testing,  Fault  Finding,  etc.,  for  Wiremen.     (Installation 

Manuals  Series.) i6mo,  *o  50 

Wright,  T.  W.     Elements  of  Mechanics 8vo,  *2  50 

Wright,  T.  W.,  and  Hayford,  J.  F.    Adjustment  of  Observations.  ..8vo,  *3  oo 
Wynne,  W.  E.,  and  Sparagen,  W.     Handbook  of  Engineering  Mathe- 
matics     8vo,  *2  oo 

Yoder,  J.  H.,  and  Wharen,  G.  B.    Locomotive  Valves  and  Valve  Gears, 

8vo,  *3  oo 

Young,  J.  E.    Electrical  Testing  for  Telegraph  Engineers 8vo,  *4  oo 

Young,  R.   B.     The   Banket 8vo,  3  50 

Youngson.     Slide  Valve  and  Valve  Gears 8vo,  3  oo 

Zahner,  R.    Transmission  of  Power.     (Science  Series  No.  40.)..i6mo, 

Zeidler,  J.,  and  Lustgarten,  J.     Electric  Arc  Lamps 8vo,  *a  oo 

Zeuner,  A.    Technical  Thermodynamics.    Trans,  by  J.  F.  Klein.     Two 

Volumes 8vo,  *8  oo 

Zimmer,  G.  F.    Mechanical  Handling  and  Storing  of  Materials.  ..  .4to,  *i2  50 

—  Mechanical    Handling   of   Material    and    Its   National   Importance 

During  and  After  the  War 4to,  4  oo 

Zipser,  J.  Textile  Raw  Materials.  Trans,  by  C.  Salter 8vo,  *6  25 

Zur  Nedden,  F.  Engineering  Workshop  Machines  and  Processes.  Trans. 

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